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chemical engineering research and design 8 9 ( 2 0 1 1 ) 136147

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Chemical Engineering Research and Design
j our nal homepage: www. el sevi er . com/ l ocat e/ cher d
Design of experiments for statistical modeling and
multi-response optimization of nickel electroplating process
Maria Poroch-Seritan
a
, Sonia Gutt
a
, Gheorghe Gutt
a
, Igor Cretescu
b,
,
Corneliu Cojocaru
b,
, Traian Severin
a
a
S tefan cel Mare University of Suceava, Faculty of Food Engineering, 9 Universit atii street, 720225, Suceava, Romania
b
Gheorghe Asachi Technical University of Ias i, Department of Environmental Engineering and Management, 71 Mangeron Blvd.,
700050, Iasi, Romania
a b s t r a c t
The central composite experimental design and response surface methodology have been employed for statistical
modeling and analysis of the results dealing with nickel electroplating process. The empirical models developed in
terms of designvariables (current density J (A/dm
2
), temperature T (

C) andpH) have beenfoundstatistically adequate


todescribe the process responses, i.e. cathode efciency Y(%), coating thickness U(m), brightness V(%) andhardness
W(HV). The graphical representations consistedof 2Dcontour plots and3Dsurface plots have beenusedfor exploring
and analysis of response surfaces in order to identify the main, quadratic and interaction effects. The multi-response
optimization of nickel electroplating process has been carried out by means of desirability function approach. To
this end, a genetic algorithm has been used for mathematical optimization of the multi-response problem. The
optimization algorithm has conducted to a set of equivalent solutions named Pareto optimal set. The conrmation
runs have been employed in order to make a decision about the optimal solution approved by experiment. Thus,
the optimum conditions of nickel electroplating has been dened in this work as J* =5.35 (A/dm
2
), T* =33.44 (

C) and
pH* =6.22 and respectively the responses conrmed by experiment were Y=79.120.18 (%), U=52.770.48 (m),
V=26.120.45 (%) and W=371.61.77 (HV). In such conditions the quality of nickel electroplating deposit was the
best one in accordance with experimental results.
2010 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Keywords: Electroplating; Experimental design; Response surface method; Desirability function; Genetic algorithm
1. Introduction
Nickel electroplating is used extensively for decorative, engi-
neering and electroforming purposes. Decorative applications
account for about 80% of nickel consumption in plating while
20% is consumed for engineering and electroforming aims (Di
Bari, 2000).
The environmental aspects related to electroplating indus-
try such as waste minimization, toxicity of electroplating
metals and reduction of both chemicals and water con-
sumption have been deeply approached by different authors
(Abou-Elela et al., 1998; Babu et al., 2009; Fang and Chan, 1997;
Kuntay et al., 2006).

Corresponding author. Tel.: +40 741914342; fax: +40 32 271311.

Corresponding author. Tel.: +40 742176747.


E-mail addresses: icre@ch.tuiasi.ro (I. Cretescu), cojocaru c@yahoo.com (C. Cojocaru).
Received24 November 2009; Receivedinrevisedform11 May 2010; Accepted28 May2010
In the last decades, many scientic and technical studies
have been carried out to account for the effects of factors
on electroplating performance and to address the enhance-
ment of nickel electroplating process (Abd El Wahaab et
al., 1986; Dolgikh et al., 2009; Njau et al., 1998; Tsuru et
al., 2002; Hoffmann et al., 2008; Gupta et al., 2002; Yoshida
et al., 2003, 2004; Abdel-Hamid, 1998; Wang et al., 2008;
Shpanko et al., 2004; Badarulzaman et al., 2009; Balakai et
al., 2009; Sotskaya and Dolgikh, 2008; Mohanty et al., 2001;
Ciszewski et al., 2004; Oliveira et al., 2006; Orinakova et al.,
2006). However, it is worth to mention that most of such
investigations dealt with conventional methodology of exper-
imentation in which one factor is varied while others are xed
at constant levels. The classical methods of experimentation
0263-8762/$ see front matter 2010 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.cherd.2010.05.010
chemical engineering research and design 8 9 ( 2 0 1 1 ) 136147 137
Nomenclature
a
i1
, a
i2
, coefcients for desirability function
b
0
, b
i
, b
ii
, b
ij
regression coefcients for polynomial equa-
tions
b vector of regression coefcients
d individual desirability function
D overall desirability function
D

black intensity of sample


F ratio of variances (Fischer test)
g population size for GA (integer number)
I current intensity
i and j subscripts (integer variables)
J current density
k iteration indicating the current population in
GA
L number of signicant regression coefcients
m integer number (m<g)
m
p
experimental amount of nickel deposition
m
t
theoretical amount of nickel deposition
n number of variables
n
0
number of experiments in center point
N number of experimental runs in CCD
p level of signicance
R reection (relative percent)
R

intensity of standard reference substance


s number of responses
S
2
0
error mean square
S
2
res
residual mean square
S

intensity of sample
T temperature
t time of electrolysis
U average thickness of metallic layer (experimen-
tal value)

U average thickness of metallic layer (predicted


value)
V brightness of metallic coating (experimental
value)

V brightness of metallic coating (predicted value)


W hardness of metallic coating (experimental
value)

W hardness of metallic coating (predicted value)


X matrix of experimental design
x vector of variables (coded values)
x
(k)
cj
chromosome (vector of variables in GA)
x
(k)
pj
parent chromosome (vector of variables in GA)
y response (general term)
y
0i
response recorded in the center point
y
0
average value of response
y predicted values of response
y response vector
Y cathode efciency (experimental value);

Y cathode efciency (predicted value by regres-


sion model);
z actual value of design variable
z
0
center point of design variable (actual value)
z interval of variation for design variable
* superscript indicating optimal value
Greek letters
axial point or star point in CCD;
wavelength

1
,
2
degree of freedoms
valid region (initial region of experimentation)
usually ignore the interaction effects between variables (fac-
tors) and lead to the counterfeit optimal conditions. In order
to overcome this issue the response surface methodology
(RSM) may be used. This methodology (RSM) is a collec-
tion of mathematical and statistical techniques useful for
developing, improving, and optimizing processes that can
be used to assess the relative signicance of several inde-
pendent variables (factors) even in the presence of complex
interactions. According to RSM strategy, the tting of exper-
imental data to a proper response surface model must be
performed based on statistical design of experiments. After-
wards, the developed mathematical model is used to establish
the optimum operational conditions of the process under
investigation.
Few studies related to implementation of experimental
design for nickel plating process have been reported in litera-
ture (Oraon et al., 2006; Hu and Bai, 2001a, 2001b).
Oraon et al. (2006) have applied the response sur-
face method for predicting of electroless nickel plating
process. In this respect, authors have used a central
composite design (CCD) for experimentation. It has been
observed that reducing agent (NaBH
4
), source of metal
(NiCl
2
6H
2
O) and temperature signicantly affect the deposi-
tion.
The authors (Hu and Bai, 2001a) have studied the com-
position control of electroplated nickelphosphorus deposits.
To this end, the inuences of electroplating variables, such
as temperature, current density, pH, NaH
2
PO
2
H
2
O concentra-
tion and agitation rate, on the phosphorus content of NiP
deposits electroplated from a Watts nickel bath modied with
NaH
2
PO
2
H
2
O were systematically compared using fractional
factorial design (FFD).
In addition, the same authors (Hu and Bai, 2001b) have
optimized hydrogen evolving activity on nickelphosphorus
deposits using experimental strategies. In this regard, the
effects of electroplating variables on the hydrogen evolving
activity of NiP deposits were systematically examined using
fractional factorial design (FFD), path of steepest ascent, and
central composite design(CCD) coupledwiththe response sur-
face method (RSM). The FFDstudy indicated that the mainand
interactive effects of temperature, pH, and NaH
2
PO
2
H
2
O con-
centration are the key preparation factors inuencing the NiP
cathode.
The implementation of statistical experimental design
techniques for electroplating process assisted by develop-
ing of empirical models may conduct to an enhanced
electroplating performance and to reduction of overall
costs of experimentation. To the best of our knowledge,
there is a lack of reports in the literature regarding
multi-response optimization of nickel electroplating process.
Therefore, this work deals with statistical modeling and
multi-response optimization of nickel electroplating process
in order to improve the cathode efciency as well as to
obtain the best characteristics of the electroplated covers
in terms of thickness, brightness and hardness of metallic
layer.
138 chemical engineering research and design 8 9 ( 2 0 1 1 ) 136147
Table 1 Chemical composition of Watts-type bath used
for nickel electroplating.
Chemical composition Concentration (g/L)
Nickel chloride, NiCl
2
6H
2
O 40.5
Nickel sulfate, NiSO
4
6H
2
O 292.5
Boric acid, H
3
BO
3
31.5
2. Experimental
Electroplating experiments were carried out using a Watts-
type bath. Details of the bath composition employed are
given in Table 1. All chemicals used in electroplating exper-
iments were of analytical reagent grade. Solution of sodium
hydroxide (0.01N) was used for pH adjustment. The home
made electrochemical cell was employed for nickel electro-
plating experiments. The dimensions of cell are as follows:
13.9cm (length) 12.5cm (width) 10cm (height), correspond-
ing to a volume of 1.75L. In addition, the cell was equipped
with a cathode (made of 99.98% purity copper) and an
anode (made of 99.7% purity nickel). The cathode dimen-
sions are of 8.0cm (height) 9.8cm (length) 0.1cm (width)
while the dimensions of anode were of 10.0cm(height) 4.0cm
(length) 0.3cm (width). The immersion surface of cathode
was of 0.6dm
2
and respectively the anodic immersion sur-
face was of 0.25dm
2
. The above-described cell was connected
in galvanostatic regime to the GWINSTEK GPR-1810HD power
supply, having a digital control of current and voltage.
The temperature of electrolyte solution was kept constant
using the Lauda E100 thermostatic bath. Before each elec-
troplating experiment the cathode surface was prepared
accordingly.
The performance of nickel electroplating process was esti-
mated in terms of four responses, namely, cathode efciency,
Y (%); average thickness of metallic layer, U (m); brightness
of metallic coating, V (%) and hardness of metallic coating, W
(HV).
The cathode efciency, Y (%), was determined by using Eq.
(1):
Y =
m
p
m
t
100 =
m
p
3.041 10
4
I t
(1)
where m
p
denotes the experimental amount of nickel depo-
sition (g); m
t
the theoretical amount of nickel deposition (g);
I the current intensity which cross the electrical circuit (A); t
time of electrolysis (s); 3.04110
4
(g/C) is the electrochemical
equivalent of nickel (Paunovic and Schlesinger, 2006; Popov et
al., 2002).
The thickness of metallic layer was measuredby means of a
PosiTector 6000 DeFesko Analyzer, based on non-destructive
physical method. To this end, seven local values of cathode
thickness were measured in order to determine the average
thickness of metallic layer, U (m).
The brightness of metallic cover V (%) was evaluated using
the HR 4000 CG-UV-NIR spectrometer (Ocean Optics Inc.,
Dunedin, FL) based on the reection property of the deposed
metallic layer. In this respect, the scanning with 0.025nm
resolutionhas beencarriedout for the entire wavelengthspec-
trumranged from200 up to 1100nm. Atungsten halogen light
source (UV-VIS-NIR Light Source DH-2000, Mikropack) was
used for this study. The experimental data were displayed and
stored using the operating software OOI Base32 from Ocean
Optics. The light from Light Source DH-2000 was conveyed to
the sample through an array of optical bers (QR400-7-UV/BX,
Ocean Optics Inc., Dunedin, FL).
The reection was quantied as a relative percent (R)
fromthe reectionof standard reference substance STAN-SSH
(STAN-SSH High-reectivity Specular Reectance Standard,
Ocean Optics Inc.), according to Eq. (2):
R =
S

100% (2)
where S

means the intensity of sample at wavelength ; D

the black intensity of sample at wavelength ; R

is the inten-
sity of standard reference substance at wavelength .
The reections were measured at the wavelengths, where
the visual sensibility is maximal one, i.e. 420nm (blue),
534nm (green) and 564nm (yellow), and by considering three
points from the electrode surface. The nal reported value of
brightness V (%) represents the average value of reections
determined based on nine measurements as described previ-
ously.
The hardness of metallic coating, W (HV), was measured
using the Shimadzu, HMV 2T, micro-hardness tester. The
loading weight was of 490.3mN and the load duration of 15s.
3. Results and discussion
3.1. Statistical modeling of electroplating process
The statistical method of experimentation was employed for
modeling and optimization of the electroplating process. The
applying of statistical method is useful to understand the
interaction effects between factors and to reduce the total
number of experimental runs by saving time and adjacent
costs.
The most signicant design variables (key factors) that
inuence the performance of nickel electroplating process
deals with current density, J (A/dm
2
); temperature, T (

C); and
pH value of the solution. The signicance of these factors as
well as their operating range was deduced based on the pre-
liminary experimental tests (not shown in the manuscript).
The importance of each selected factor is discussed briey in
the following.
The current density, J (A/dm
2
), is a key factor for two main
reasons. Firstly, the current density controls the rate of depo-
sition (Rose and Whittington, 2002). Secondly, the current
density must be controlled within the correct operating range
in order to obtain sound deposits having uniform appearance
and free from burning or treeing. For optimum productivity
it will be desirable to operate with the desired current den-
sity and the available current. In practice, the size, shape or
weight of the work may limit the surface area that can be
loaded. In such cases, the current may need to be reduced
to achieve the desired current density. The control of current
density is particularly critical where work is being plated to
a specied thickness and the equipment operates on a xed
time cycle. Thus, in electroplating, current density and its dis-
tribution play a centrally important role in determining the
quality of the nal deposit (Paunovic and Schlesinger, 2006).
Changes in temperature can affect the performance of
nickel plating and other process solutions. Specically, tem-
perature can inuence the brightness range, throwing power,
ductility, hardness, internal stress and burning characteristics
(Di Bari, 2000; Rose and Whittington, 2002).
chemical engineering research and design 8 9 ( 2 0 1 1 ) 136147 139
Table 2 Correspondence between actual and coded values of design variables.
Design variables Symbol Actual values of coded levels Step of variations
1 0 +1 +
J, current density (A/dm
2
) x
1
1.33 1.66 3.33 5 5.36 1.66
T, temperature (

C) x
2
11.77 15 30 45 48.22 15
Solution pH x
3
3.78 4 5 6 6.22 1
The solution pH is a measure of the hydrogen ion concen-
tration, or more simply the acidity, of a solution. In the case
of nickel solutions the pH has an important inuence on bath
performance. The pHcan affect the bright plating range, cath-
ode efciency, effects of impurities, throwing power, stress
as well as the physical properties of the deposit (Rose and
Whittington, 2002).
For statistical calculations the actual values of variables
were scaled-up (coded) according to Eq. (3) (Akhnazarova and
Kafarov, 1982; Myers and Montgomery, 2002):
x
i
=
z
i
z
0
i
z
i
i = 1, n (3)
where z denotes the actual value of design variable; z
0
the
center point of designvariable (actual value); z the interval of
variation; x the coded level of design variable (dimensionless
value) and n is the number of variables. Basically, the extent
of each variable involves three different coded levels from low
(1) to medium (0) and to high (+1). In addition, depending on
the type of experimental design, the axial levels () can be
considered.
The operating region and the levels of the design variables
(key factors) are giveninactual and coded values as it is shown
in Table 2. A central composite design (CCD) of orthogonal
type was employed in this study to perform the electroplating
experiments in a systematically manner by varying simulta-
neously all the factors (Table 3). The axial level (star point)
has been computed from the condition for a CCD to be an
orthogonal design and may be written in this case as fol-
lows (Akhnazarova and Kafarov, 1982; Khuri and Cornell, 1996;
Myers and Montgomery, 2002):
=
_
_
2
n
(2
n
+2n +1) 2
n
2
_
1/2
(4)
According to the experimental design a total number of 16
experimental runs were carried out. The CCDconsists of three
distinct regions: (i) full factorial design in which the factor lev-
els are coded to the usual low (1) and high (+1) values; (ii)
axial points localized on the axis of each variable at a distance
from the designed center; and (iii) center points that can be
replicated to provide an estimation of the experimental error
variance. Four responses have been determined experimen-
tallyinaccordance withdesignedruns inorder toascertainthe
performance of the electroplating process. These responses
are related to cathode efciency, Y (%); average thickness of
metallic layer, U (m); the brightness, V (%) and the hardness,
W (HV) of metallic cover.
Commonly, a quadratic response surface model with cross
terms canbe constructed to t the experimental data obtained
in accordance with CCD. The response surface model (RS-
model), known also as regression or empirical equation,
represents a polynomial approximation of experimental data
and is stated by the following relationship:
y = b
0
+
n

i=1
b
i
x
i
+
n

i=1
b
ii
x
2
i
+
n

i<j
b
ij
x
i
x
j
(5)
where y denotes the predicted response (e.g. predicted cath-
ode efciency), x
i
the coded levels of the design variables, and
b
0
, b
i
, b
ii
, b
ij
are the regression coefcients (offset term, main,
Table 3 Central composite orthogonal design applied for electroplating experiments.
N Design variables Responses (experimental values)
Current density Temperature Solution pH Y (%) U (m) V (%) W (HV)
J (A/dm
2
) x
1
T (

C) x
2
pH x
3
1 5 +1 45 +1 6 +1 100 47.85 24.71 346.00
2 1.66 1 45 +1 6 +1 99.48 35.86 1.99 289.20
3 5 +1 15 1 6 +1 85.56 33.43 17.91 218.10
4 1.66 1 15 1 6 +1 99.10 42.57 21.76 336.00
5 5 +1 45 +1 4 1 99.27 30.29 2.50 228.10
6 1.66 1 45 +1 4 1 99.70 38.86 3.96 237.90
7 5 +1 15 1 4 1 97.05 38.00 9.36 214.00
8 1.66 1 15 1 4 1 98.67 41.43 16.38 273.00
9 5.36 + 30 0 5 0 100 43.57 37.13 343.70
10 1.33 30 0 5 0 98.18 35.86 3.49 271.70
11 3.33 0 48.22 + 5 0 97.07 33.57 4.15 237.10
12 3.33 0 11.77 5 0 99.73 38.29 11.00 211.50
13 3.33 0 30 0 6.22 + 96.99 58.29 15.39 502.90
14 3.33 0 30 0 3.78 100 34.14 25.19 318.40
15 3.33 0 30 0 5 0 99.10 33.71 3.27 248.00
16 3.33 0 30 0 5 0 98.82 34.30 4.20 252.5
140 chemical engineering research and design 8 9 ( 2 0 1 1 ) 136147
Fig. 1 Comparison between experimental data and mathematical models related to cathode efciency Y (%) and brightness
V (%) of metallic layer.
quadratic and interaction or cross effects). The least square
estimations of the regressioncoefcients have beencomputed
by means of ordinary least squares (OLS) method and can be
written as follows (Akhnazarova and Kafarov, 1982; Myers and
Montgomery, 2002; Bezerra et al., 2008):
b =(X
T
X)
1
X
T
y (6)
where b is a vector of regression coefcients, X the design
matrix of the coded levels of input variables, and y is a col-
umn vector of response determined experimentally according
to the arrangement points into CCD.
Based on experimental design results (Table 3) the regres-
sion models have been constructed by means of OLS-method
in order to determine the functional relationship for approx-
imation and prediction of responses. Thus, the second-order
RS-models with coded variables obtained for Ni electroplating
process are as follows:

Y = 97.99 1.174x
1
+1.355x
2
1.297x
3
+1.906x
1
x
2
1.371x
1
x
3
+1.446x
2
x
3
(7)

U = 38.42 +3.695x
3
3.055x
2
2
+3.918x
2
3
+1.999x
1
x
2
+2.249x
2
x
3
(8)

V = 17.2 +4.68x
1
3.704x
2
5.462x
2
2
+4.016x
1
x
2
+3.419x
1
x
3
(9)

W = 299.2 +42.04x
3
72.85x
2
2
+53.49x
2
3
+27.99x
1
x
2
(10)
subjected to: x
i
; ={x
i
|x
i
+}; i = 1, 3
Note that, the term denotes the valid region (region of
experimentation) where the regression models are valid over.
The signicance of regressioncoefcients was testedusing the
statistical Students t-test. Thus, inEqs. (7)(10) only the signif-
icant terms were retained. Figs. 1 and 2 show the comparison
between experimental data and predicted data provided by
regression models.
For testing the goodness-of-t of regression equations, the
statistical Fisher F-test was employed considering the signif-
icance level of p=0.05. In this regard, one must compute the
error mean square and residual mean square. The error mean
square (S
2
0
) that has been calculated by using the repeated
observations (Akhnazarova and Kafarov, 1982; Gavrilescu and
Tudose, 1999):
S
2
0
=
1
n
0
1
n
0

i=1
(y
0i
y
0
)
2
(11)
where n
0
is the number of experiments in center point (repro-
ducibility), y
0i
denotes the values of response recorded in the
center point and y
0
is the average value of y
0i
. The residual
mean square (S
2
res
) has been computed as (Akhnazarova and
Kafarov, 1982; Gavrilescu and Tudose, 1999):
S
2
res
=
1
N L
N

j=1
(y
j
y
j
)
2
(12)
Fig. 2 Comparison between experimental data and mathematical models related to hardness W (HV) and thickness U (m)
of metallic layer.
chemical engineering research and design 8 9 ( 2 0 1 1 ) 136147 141
Table 4 Statistical test for evaluation of model adequacy.
Model Signicant
level
Degrees of
freedom
Fischer test
(calculate value)
Fischer test
(tabulate value)
Model
adequacy

Y (x
1
, x
2
, x
3
) p=0.05
1
= N L = 8
2
= N
0
1 = 1 F
c
=
S
2
conc.
S
2
0
= 215.7 F
tab(p,1,2)
=238.9 F
c
<F
tab(p,1,2)

U (x
1
, x
2
, x
3
) p=0.05
1
= N L = 9
2
= N
0
1 = 1 F
c
=
S
2
conc.
S
2
0
= 236.1 F
tab(p,1,2)
=240.5 F
c
<F
tab(p,1,2)

V (x
1
, x
2
, x
3
) p=0.05
1
= N L = 9
2
= N
0
1 = 1 F
c
=
S
2
conc.
S
2
0
= 214.9 F
tab(p,1,2)
=240.5 F
c
<F
tab(p,1,2)

W (x
1
, x
2
, x
3
) p=0.05
1
= N L = 10
2
= N
0
1 = 1 F
c
=
S
2
conc.
S
2
0
= 213.0 F
tab(p,1,2)
=241.9 F
c
<F
tab(p,1,2)
where N is the number of observations (experimental runs), L
is the number of signicant coefcients inthe regressionequa-
tion, y
j
is the response (experimental value) and y
j
denotes the
predicted values of response according to regressionequation.
Note that, the regression model is an adequate t to the exper-
imental data if the F-ratio is smaller than the tabulated value
one F
tab(p,1,2)
(Akhnazarova and Kafarov, 1982; Gavrilescu and
Tudose, 1999):
F =
S
2
res
S
2
0
< F
tab(p,1,2)
(13)
The results of F-ratio test are focused in Table 4 for all
regression models. According to these results, the F-ratio is
lower than tabulated value in all cases revealing the adequacy
of the regression equations fromstatistical standpoint, i.e. the
models can be used for the predictions.
It is of real interest passing from regression equations with
codedvariables to mathematical models withactual variables.
To this end, the nal empirical models were obtained by sub-
stitution technique and are presented in Eqs. (14)(17):

Y = 112.5 +1.121J 0.6457T 1.448pH +0.07622J T


0.8224J pH +0.0964T pH (14)

U = 136.2 2.398J 0.2015T 39.98pH 0.01358T


2
+3.918pH
2
+0.07994J T +0.1499T pH (15)

V = 43.64 12.27J +0.6743T 6.836pH 0.02428T


2
+0.1606J T +2.051J pH (16)

W = 1247 33.58J +15.7T 492.9pH 0.3238T


2
+53.49pH
2
+1.119J T (17)
where J, T and pH are the real values of independent variables
related to current density (A/dm
2
), temperature (

C), and pH
value of solution, respectively. The valid region in actual space
is dened by the following set of constraints:
1.33J 5.36 (current density, A/dm
2
);
11.77T48.22 (temperature,

C);
3.78pH6.22 (pH of solution).
Eqs. (14)(17) have been used for simulation (predictions)
and graphical representations of response surfaces as it is
shown in Figs. 310.
Figs. 3 and 4 show the response surface plot of the cathode
efciency Y (%) as a function of design variables. In addi-
tion to main effects, the interaction effects between factors
are considerable. Thus, at lower values of temperature the
increment of current density J (A/dm
2
) conducts to straight
decreasing of cathode efciency, while for higher tempera-
ture levels the growth of current density leads to slightly
increasing of this response. Concerning the inuence of tem-
perature, the cathode efciency goes up with increasing of
temperature, especially at higher levels of current density.
For low levels of current density the increment of temper-
ature conducts to slightly decreasing of cathode efciency.
The inuence of pH is also affected by interaction effects
between variables. As one can see, the increasing of solu-
tion pH leads to descent of cathode efciency, especially
at higher levels current density. For low values of current
density the inuence of pH becomes insignicantly. There
are no quadratic effects of the factors on cathode efciency
response.
Figs. 5 and 6 illustrate the response surface plots and
contour-lines maps in case of the brightness V (%) of nickel
deposition. Owing to strong quadratic effect, an optimal value
of temperature is observed in the range of 3036

C leading
to the maximum level of the brightness. The increment of
solution pH conducts to improving of the brightness. Due to
the main effect, the increasing of current density leads to
enhancement of the brightness. The improving of brightness
withcurrent density is especially conspicuous at higher values
of temperature.
Response surfaces and contour curves illustrated in
Figs. 7 and 8 highlights the effects of design variables on
performance criterion W (Vickers hardness). In this case, the
increasing of solution pH leads to improving of deposit hard-
ness. Because of strong quadratic effect, the optimum range
of temperature is located in the limits of 3036

C where the
Vickers hardness is the highest. The effect of current density
on hardness is the lowest one if compared with the effects of
other two variables. This effect is due to interaction between
temperature and current density. Thus at low values of tem-
perature, the increment of current density leads to a minor
decrease of the response, W (HV). While at high levels of
temperature the increasing of current density cause a slight
improving of hardness.
In Figs. 9 and 10 are shown the response surfaces related to
the thickness of electroplated layer, U (m). One can observe
that in this case, pH of solution has the greatest inuence on
the response. More precisely, the increment of pH in the range
studied contributes to the evident growth of the thickness U
(m). Due to quadratic effect associated with temperature fac-
tor, there is a ridge-type surface with a maximum visible in
the range of 2040

C. The inuence of current density is dom-


inated by the effect of interaction. Thus, for low temperature
(<25

C), the increment of current density leads to diminishing


of thickness. By contrast, at high levels of temperature (>30

C)
142 chemical engineering research and design 8 9 ( 2 0 1 1 ) 136147
Fig. 3

Y response surface plot and contour-lines map depending on T (

C) and J (A/dm
2
) variables, holding the third
variable at xed level, pH 5.0.
Fig. 4

Y response surface plot and contour-lines map depending on pH and J (A/dm
2
) variables, holding the third variable
at xed level, T=30

C.
the increasing in current density conducts to growth of the
thickness.
3.2. Optimization of electroplating process
The optimization of a process described by two or more
responses, it is helpful to carry out by using the concept
of desirability function. According to this methodology, each
response y
i
must be converted into the individual desirabil-
ity function d
i
that ranges from 0 (very undesirable) to 1 (very
desirable). Such transformation may be presented as follows
(Akhnazarova and Kafarov, 1982):
d
i
( y
i
(x)) = exp[exp((a
i1
+a
i2
y
i
(x)))] i = 1, s (18)
where s is the number of responses involved (in our spe-
cic case s =4); the coefcients a
i1
and a
i2
were calculated by
assigning for two values of y
i
the corresponding two values
of d
i
, preferably in the range 0.2<d
i
<0.8 (Akhnazarova and
Kafarov, 1982).
Afterwards, the individual desirability values are combined
into the overall desirability function, D, which is computed as
Fig. 5

V response surface plot and contour-lines map depending on pH and T (

C) variables, holding the third variable at


xed level, J =3.33A/dm
2
.
chemical engineering research and design 8 9 ( 2 0 1 1 ) 136147 143
Fig. 6

V response surface plot and contour-lines map depending on J (A/dm
2
) and T (

C) variables, holding the third


variable at xed level, pH 5.0.
Fig. 7

W response surface plot and contour-lines map depending on pH and T (

C) variables, holding the third variable at


xed level, J =3.33A/dm
2
.
geometric mean (Derringer and Suich, 1980; Akhnazarova and
Kafarov, 1982; Khayet et al., 2008):
D(x) = [d
1
( y
1
(x)) d
2
( y
2
(x)) d
s
( y
s
(x))]
1/s
(19)
If an individual desirability function is completely unde-
sirable, i.e. d
i
=0 then the value of overall desirability is
nullied. In case of nickel electroplating process discussed in
the present paper, the overall desirability function approach
combines four responses, namely, the cathode efciency,
thickness, brightness and hardness of nickel deposition and
may be written in extended form as follows:
D(x
1
, x
2
, x
3
) = exp{(1/4) [exp((6.731 +0.075

Y(x
1
, x
2
, x
3
)))
+exp((1.495 +0.039

U(x
1
, x
2
, x
3
)))
+exp((0.387 +0.031

V(x
1
, x
2
, x
3
)))
+exp((1.111 +3.71 10
3


W(x
1
, x
2
, x
3
)))]}
(20)
The formulation of multi-response optimization problem
in this case is related to maximization of desirability function
Fig. 8

W response surface plot and contour-lines map depending on J (A/dm
2
) and T (

C) variables, holding the third


variable at xed level, pH 5.0.
144 chemical engineering research and design 8 9 ( 2 0 1 1 ) 136147
Fig. 9

U response surface plot and contour-lines map depending on pH and T (

C) variables, holding the third variable at


xed level, J =3.33A/dm
2
.
and may be written as:
max
x
D(x)
= max
_
_
d
1
(

Y(x)) d
2
(

U(x)) d
3
(

V(x)) d
4
(

W(x))

1/4
, x
_
(21)
Note, that, the solving of multi-response optimization
problem dened by Eq. (21) involves guring out of a solu-
tion in the design space that satises several specications
(objectives) in the performance space of responses. Usually,
such specications are conicting and there is no simulta-
neous optimal solution for all of them. In this respect, the
solution is not unique; instead there is a set of possible solu-
tions where none is best for all responses. Such set of possible
optimal solutions in the design space is called Pareto optimal
set (Blasco et al., 2008). The Pareto optimality is a condition
when a single response cannot be improved without damag-
ing the qualities of other responses. The region dened by the
responses for all Pareto set points is called the Pareto optimal
front. In fact, the Pareto front supplies a set of solutions where
the designer (decision-maker, experimentalist) has to look for
the best choice according to his preferences. In order to g-
ure out Pareto optimal set, a genetic algorithm (GA) has been
employed for mathematical optimization.
Genetic algorithms (GAs) are a special class of evolutionary
algorithms (EA) that make use of random search techniques
inspired from evolutionary processes in nature (e.g. natural
selection and genetics) (Pasandideh and Niaki, 2006; Hibbert,
1993; Leardi, 2007).
GA involves a series of successive steps (Renner and Ekrt,
2003; Yuan and Qian, 2010; Preechakul and Kheawhom, 2009;
Shopova and Vaklieva-Bancheva, 2006) that are given in the
owchart shown in Fig. 11. The algorithm starts with initial-
ization of the rst population. Thus, it creates a rst current
population {x
(k)
c1
, x
(k)
c2
, . . . , x
(k)
cg
} with g number of individuals
(population size) where k denotes the iteration number also
known as generation. Each individual x
(k)
cj
in the population is
called a chromosome and represents a solution to the prob-
lem. Traditionally, solutions are represented in encoded form
as binary strings of 0s and 1s, but other encodings are also
possible including real code. Each individual in the current
population is evaluated in terms of tness value. Note that,
according to GA terminology the tness function is identical
with the objective function or desirability function in our case.
The tness evaluation of the current population may be noted
as
_
D
_
x
(k)
c1
_
, D
_
x
(k)
c2
_
, . . . , D
_
x
(k)
cg
__
. Afterwards, the termi-
nation criterion is veried. If it is met, the best solution is
then returned. As usually, the termination criterion allows at
most a predened number of iterations and veries whether
an acceptable solution was found (Renner and Ekrt, 2003).
If the termination criterion is not satised, then, some indi-
viduals are selected from the current population based on
the tness values. Such selected individuals are named par-
ent chromosomes
__
x
(k)
p1
_
,
_
x
(k)
p2
_
, . . . ,
_
x
(k)
p(gm)
__
and are used
Fig. 10

U response surface plot and contour-lines map depending on J (A/dm
2
) and T (

C) variables, holding the third


variable at xed level, pH 5.0.
chemical engineering research and design 8 9 ( 2 0 1 1 ) 136147 145
Fig. 11 The owchart of the genetic algorithm.
for generation of new chromosomes (offspring) that make
a new population
__
x
(k+1)
c1
_
,
_
x
(k+1)
c2
_
, . . . ,
_
x
(k+1)
cg
__
. To this
end, the genetic operators like reproduction, crossover and muta-
tion are used to generate a new population (Pasandideh and
Niaki, 2006; Hibbert, 1993; Leardi, 2007; Renner and Ekrt,
2003; Yuan and Qian, 2010; Preechakul and Kheawhom, 2009;
Shopova and Vaklieva-Bancheva, 2006). Generally, implemen-
tations of genetic algorithms differ in the mode of constructed
new population. In this work, the population size used in GA
optimizationwas of g =20. Inorder to developnewgenerations
the genetic operators were used in the following proportion:
reproduction (10%), mutation (20%) and crossover (70%).
The results of optimization (Pareto optimal set) given by
GA are displayed in Table 5. The set of optimal solutions
determined by mathematical calculation contains 5 points
(solutions) that are localized on Pareto front. The desirabil-
ity function scores in these points (tness values) are ranged
from 0.509 to 0.529 pointing out that all these points are of
interest. However, selecting a single solution as the optimal
point for process is a matter of decision that depends on spe-
cialist preferences. In this acceptation, the sensitivity analysis
and experimental conrmation plays an essential role.
In our case, the emphasis was placed on the experimental
conrmation of Pareto solutions. After experimental verica-
tion, the best experimental runis the point O3 being denedby
the following values of factors: J* =5.35 (A/dm
2
), T* =33.44 (

C)
and pH* =6.22. In such conditions the quality of nickel electro-
plating deposit (layer) was the best one being superior over the
other points fromPareto optimal set. Note that, for other solu-
tions fromPareto set (i.e. O1, O2, O4 and O5) the electroplating
layers obtained experimentally are of lower quality. More pre-
Table 5 Pareto optimal solutions.
No. Design variables (factors) Responses (performance criteria) Desirable function
Current density Temperature pH

Y

U

V

W D
O1 x
1
=1.211J =5.35A/dm
2
x
2
=0.104T=31.56

C x
3
=1.215pH=6.22 93.537 49.194 27.961 431.96 0.514
O2 x
1
=1.202J =5.34A/dm
2
x
2
=0.806T=42.09

C x
3
=1.215pH=6.22 97.357 50.843 25.174 408.95 0.529
O3 x
1
=1.211J =5.35A/dm
2
x
2
=0.229T=33.44

C x
3
=1.215pH=6.22 94.215 49.712 27.879 433.17 0.520
O4 x
1
=1.211J =5.35A/dm
2
x
2
=0.104T=31.56

C x
3
=1.215pH=6.22 93.537 49.194 27.961 431.96 0.514
O5 x
1
=0.601J =4.34A/dm
2
x
2
=0.408T=36.12

C x
3
=1.169pH=6.17 96.515 49.143 20.979 416.10 0.509
146 chemical engineering research and design 8 9 ( 2 0 1 1 ) 136147
Table 6 Experimental conrmation of optimal solution
O3, J =5.35A/dm
2
, T=33.44

C, pH=6.22.
Y (%) U (m) V (%) W (HV)
Run 1 79.09 52.71 26.10 370.0
Run 2 79.31 52.33 26.57 371.3
Run 3 78.95 53.28 25.68 373.5
Mean value 79.12 52.77 26.12 371.6
S.D. 0.18 0.48 0.45 1.77
cisely, suchlayers were non-uniformand had a week adhesion
to the substrate.
Table 6 shows the experimental values of responses deter-
mined under the conditions given by point O3, i.e. J =5.35
(A/dm
2
), T=33.44 (

C) and pH=6.22. Three replication runs


were performed in these conditions and the mean values of
responses as well as their standard deviations (S.D.) are also
reported in Table 6. Thus, the optimal solution O3 is described
by the following mean values of responses conrmed exper-
imentally (Table 6): Y=79.120.18 (%), U=52.770.48 (m),
V=26.120.45 (%) and W=371.61.77 (HV). As one can
deduce, the optimal condition conrmed experimentally rep-
resents a compromise between involved responses and have
conducted to a high quality properties of metallic deposition.
All computations were performed using Matlab software as
a tool for scientic programming and technical calculations.
4. Conclusions
In the present work it was demonstrated the applicabil-
ity of experimental design, response surface methodology
and desirability function approach for modeling and multi-
response optimization of nickel electroplating process.
Based on the experimental design results, the second-
order polynomial models were developed for predicting the
electroplating responses (i.e. cathode efciency Y (%), coating
thickness U (m), brightness V (%) and Vickers hardness W
(HV)) as a functional combination of design variables, namely
current density J (A/dm
2
), temperature T (

C) and pH of the
solution. The polynomial models were statistically validated
using F-ratio test. The graphical response surfaces analy-
sis was employed for identication and discussion of main,
quadratic and interaction effects of factors on responses.
A global objective function (desirability function) was
constructed for multi-response optimization. In order to
solve the multi-response problem a genetic algorithm was
employed. The results of optimization offered a set of solu-
tions known as Pareto optimal front. The mathematical
solutions were veried via experimentation and the best
experimental conditions were established. The optimal solu-
tion conrmed by experiment involves the following levels
of factors: J* =5.35 (A/dm
2
), T* =33.44 (

C) and pH* =6.22. The


desirable values of responses in these conditions are as fol-
lows: Y=79.120.18 (%), U=52.770.48 (m), V=26.120.45
(%) and W=371.61.77 (HV). As one may conclude, the opti-
mal combination of factors conducted to desirable levels of
responses, and nally to the best characteristics of the elec-
troplated cover.
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