Você está na página 1de 6

Hydrometallurgy 111112 (2012) 103108

Contents lists available at SciVerse ScienceDirect

Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Modeling and optimization of surface quality of copper deposits recovered from brass
scrap by direct electrowinning
M. Aghazadeh, A. Zakeri , M.Sh. Bafghi
School of Metallurgy and Materials Engineering, Iran University of Science and Technology, Tehran 16846-13114, I.R. Iran

a r t i c l e

i n f o

Article history:
Received 8 April 2011
Received in revised form 21 August 2011
Accepted 3 November 2011
Available online 11 November 2011
Keywords:
Scrap recycling
Copper recovery
Anodic dissolution
Electrodeposition
Cathode quality
Statistical design of experiments
Response surface methodology

a b s t r a c t
A research study has been undertaken to develop the fundamentals of a method for the direct recovery of
copper from brass (Cu30 wt.% Zn) scrap based on simultaneous electrolytic dissolution of the scrap at the
anode and electrodeposition of copper at the cathode in an acidied sulfate electrolyte. In the present
paper, effects of the concentrations of Cu 2+ (1050 g/L), Zn2+ (040 g/L) and free H2SO4 (15 N) in the electrolyte as well as cathodic current density (50350 A/m 2) and bath temperature (3070 C) have been
studied on the macroscopic surface quality of copper deposits dened by their visual morphological characteristics as expressed by an innovative Deposit Morphology Index (DMI). A Central Composite Design of experiments has been used to develop a quadratic model correlating the key operating parameters to the DMI.
Statistical analysis of the experimental results showed that the concentration of Cu 2+ in the electrolyte
and the cathodic current density are the most inuential factors on the quality of the deposits. It was also
found that these two parameters have statistically signicant interaction on each other. A smooth and compact copper deposit could be obtained at high Cu2+ concentrations and high current densities (above 40 g/L
and 250 A/m 2, respectively) regardless of the level of other factors. However, when the electrolyte temperature is relatively high (60 C), the optimum condition extends to low current densities (down to 50 A/m2)
and mid Cu 2+ concentrations (3040 g/L).
2011 Elsevier B.V. All rights reserved.

1. Introduction
Copper alloys, specially Cu30 wt.% Zn brass, have many applications in both industry and household utensils. Hence, recovery of copper and other constituents of copper alloys scraps has a considerable
economical benet. Present methods of copper recovery from these
sorts of scraps consist of smelting, re-rening and electrorening
(Davenport et al., 2002). This is a lengthy, highly energy consuming
and environmentally pollutant process.
Electrolytic recovery of metal values from alloy scraps is potentially very attractive in sense of economical and environmental considerations. Several processes have been developed using anodic
dissolution for the recovery of metals from certain alloy scraps such
as Ni-Co alloys and supperalloys (Jackson, 1986). There are a few reports concerning direct recovery of copper from its alloys through
electrolytic processes. Electrolytic recovery of copper from an alloy
scrap containing 82 wt.% copper, 7.5% tin and 10.5% other elements
has been tested in sulfate media under conditions similar to those
of the conventional copper electrorening process (Lupi and Pilone,
1998). Electrochemical recovery of copper from alloy scrap in chloride media has also been examined (Langer, 1975). Although the

Corresponding author. Tel.: + 98 21 7391 2824; fax: + 98 21 7724 0480.


E-mail address: zakeria@iust.ac.ir (A. Zakeri).
0304-386X/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2011.11.001

method has the advantage of low energy consumption, it suffers


from inverse migration of complex cuprous anions and also yields a
powdery copper deposit. Application of titanium basket for holding
copper scraps in both monopolar and bipolar cells has been examined
to bypass the copper scrap remelting and anode casting (Figueroa et
al., 1994; Gana et al., 1993). An energy saving as high as 50% has
been claimed by applying this method. Direct electrorening of cement copper in the cells equipped with a stainless steel mesh basket
as the anode-support system has also been successfully experienced
(Figueroa et al., 1997; Gana et al., 1995a, 1995b).
As regards electrolytic recovery of copper from brass scraps, however, there is almost no information available. Zinc, the main alloying
element of brass (about 30 wt.%), is supposed to dissolve anodically
together with copper, but it cannot be reduced along side with copper
in ordinary conditions, due to its much negative standard reduction
potential of 0.76 V as compared to 0.34 V for copper. Nevertheless,
it is important to understand whether and how the subsequent copper electrodeposition process and the quality of the obtained copper
deposit is affected by the presence of high concentrations of Zn 2+
ions. The knowledge from research and industrial practice indicates
that good surface quality for copper cathodes includes a smooth,
compact, non-nodular and ductile deposit. A nodular, dendritic or
rough cathode surface may cause short circuit as well as entrapment
of electrolyte and anode slimes (Dana, 1984; Davenport et al., 2002).
Although, the inuence of zinc ions on the crystal structure and

104

M. Aghazadeh et al. / Hydrometallurgy 111112 (2012) 103108

morphology of the cathodic copper in the microscopic scale have


been investigated by various researchers (Duman et al., 1989; Gana
et al., 1999; Muresan et al., 1999), it is not clear how surface quality
and macroscopic features of copper electrodeposits is affected by different process parameters in the presence of high levels of Zn 2+ ions.
In an attempt aiming at selective reclamation of a commercially
acceptable copper product by direct electrowinning from brass
scrap, an experimental study was planned and performed. The purpose of the present paper is to identify the key operating parameters
that inuence the macroscopic surface quality of copper deposits
from such process and also to nd out the optimum set of conditions
for the above mentioned objective characteristic. Effects of the
inuencing factors on other quality aspects and process measures
such as zinc impurity content, current efciency and specic energy
consumption will be presented in a forthcoming paper.
2. Experimental
2.1. Electrolysis
The electrowinning experiments were performed using stationary
electrolyte in a rectangular cell contained 1 L of acidic copper sulfate
solution containing specied amounts of Cu 2+ and Zn 2+ ions as well
as free sulfuric acid. Reagent grade sulfuric acid (Merck), distilled
water and high purity commercial grade CuSO4.nH2O and ZnSO4.nH2O
were used to make the electrolyte solutions. The reason for making
electrolyte with initial zinc sulfate additions was to simulate if the
gradual build-up of Zn 2+ ions in the electrolyte has any inuence on
the surface quality of copper deposits. Moreover, all electrolyte solutions contained 5 mg/L of each thiourea and animal glue as leveling
agents. A laboratory scale DC power supply (MEGATEK MP-3005)
was used to perform the experiments. The electrolysis cell was placed
in a water bath (Fig. 1) to ensure a constant and uniform solution temperature in the course of the experiment. Each test was conned to
2 hours to avoid possible changes in the surface quality of copper deposits due to big changes in the electrolyte composition. Anodes were
made of commercial Cu30 wt.% Zn brass sheet with a thickness of
3 mm. Two anode sheets were xed in the cell and one stainless
steel sheet in the middle as the cathode blank. Dimensions of all electrodes were 40 50 mm2. Anode to cathode spacing was xed at
about 40 mm. After termination of each experimental run, the
obtained copper deposit on the cathode substrate was thoroughly
washed with hot water and dried.
2.2. Characterization of copper deposits
Different examination techniques, such as metallographic inspection or relative density measurement, may be used to characterize
the surface goodness of copper deposits as a quality parameter.

Table 1
The conceived classication system for surface quality of copper deposits.
Deposit morphology index

Visual characteristics

1
2
3
4
5

Fully compact and smooth


Compact with nodules on cathode edges
Compact with nodules dispersed on the surface
Partly powdery
Completely powdery

However, visual inspection is the most immediate, straightforward


and economical manner, provided the visual features could be parameterized. In this research, the obtained cathode products were rst
examined by visual inspection. By setting out an innovative classication system, a Deposit Morphology Index (DMI) in a scale of 1 to 5 was
attributed to a cathode product with regard to its macroscopic surface
quality as described in Table 1. Actual pictures representing the ve
category deposits are shown in Fig. 2. Each copper deposit was then
separated from the substrate, completely dissolved in the nitric acid
solution (1 N), and analyzed for the zinc content by means of an
atomic absorption spectrometer (GBC, AVANTA ).
2.3. Design of experiments
Statistical design of experiments (DOE) is a powerful method in
materials processing studies. However, it has been rarely used in
the electrolytic processes of metals. One noticeable case is a work of
Alfantazi and Valic (2003) who have used full factorial design methodology to study copper electrowinning process. In the present
study, the Central Composite Design (CCD) methodology has been
adopted for process optimization. Usually, a response surface quadratic model as in Eq. (1) is used in a CCD.
2

y b0 bi xi bii xi bij xi xj

where y is the response, xi is the input variable and b values are the
polynomial coefcients. For the tting of a second order polynomial,
more than two levels of each variable are essential. The CCD is made
of two axial (star) points for each factor in the two-level factorial
(full or fractional) in addition to the central point with several replications. The axial points must be placed at the distances of and
from the central points. The fractional factorial design is expressed
with the symbol of 2 k p, where k is the number of variables and p
identies the type of the fractional factorial (1 for half, 2 for quarter
and so forth). The best value of for the axial points of a CCD design
to be constructed on the basis of 2 k p fractional factorial design
would be equal to 2 (k p)/4. Full explanation about the CCD could be
found in the relevant textbooks (Lazic, 2004; Montgomery, 2001). In
the present work, a 2 5 1 fractional factorial with 10 axial points and

Fig. 1. Schematic representation of the experimental set-up.

M. Aghazadeh et al. / Hydrometallurgy 111112 (2012) 103108

105

Fig. 2. Actual pictures of copper deposits on cathode substrates representing ve categories of apparent morphological features (a, b, c, d and e corresponds to a DMI of 1, 2, 3, 4 and
5, respectively). The inserts exhibit the same deposits after detachment from the substrate (not to scale).

5 centre points was used for the design. Therefore, ve levels coded by
2, 1, 0, 1 and 2 was designated for each input factor.
The likely inuential factors in the process under study are supposed to be: Cu 2+, Zn 2+ and free H2SO4 concentrations in the electrolyte, cathodic current density and electrolyte temperature, denoted
for simplicity by letters A, B, C, D and E, respectively. Based on the
knowledge obtained from the literature, suitable levels were chosen
for each parameter. The actual values corresponding to the ve levels
of each operating parameter are given in Table 2.
The quality of the deposit is seemingly difcult to incorporate into a
model or relation as emphasized by Alfantazi and Valic (2003). However, by making use of the DMI described in Table 1 as the output variable,
surface quality features of the deposits could be translated into a quantitative response, feasible for statistical data analysis and modeling. The
software Design-Expert 7.1 was employed for this purpose. A DMI of 1
that corresponds to a compact and smooth copper deposit was considered the criteria for determination of the optimum process condition.

the key response of the experimentation is given in Table 3. Preliminary statistical analysis of the results suggested that the data could
be best described by a quadratic model. A summary of the Analysis
Table 3
The design matrix and the observed DMI response for the employed CCD.

Fractional
Factorial
Points

3. Results and discussion


3.1. Modeling for DMI
The design matrix representing the experimental conditions for
the total 31 experimental runs and the corresponding DMI values as

Axial Points

Table 2
Experimental parameters and levels used in the CCD.
Operating factor

2+

Cu concentration (g/L)
Zn2+ concentration (g/L)
Free H2SO4 concentration (N)
Cathodic current density (A/m2)
Temperature (C)

Symbol

A
B
C
D
E

Level
2

10
0
1
50
30

20
10
2
125
40

30
20
3
200
50

40
30
4
275
60

50
40
5
350
70

Center Points

Standard
order

Run
order

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31

25
6
27
22
14
8
20
1
15
4
17
21
5
7
11
29
3
24
23
31
18
28
26
10
9
30
16
13
19
2
12

Coded values of operating


parameters

DMI
response

1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
2
2
0
0
0
0
0
0
0
0
0
0
0
0
0

1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
0
0
2
2
0
0
0
0
0
0
0
0
0
0
0

1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
0
0
0
0
2
2
0
0
0
0
0
0
0
0
0

1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
0
0
0
0
0
0
2
2
0
0
0
0
0
0
0

1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
0
0
0
0
0
0
0
0
2
2
0
0
0
0
0

1
1
3
1
3
1
1
1
4
1
4
1
3
1
4
1
5
1
1
1
2
1
1
2
1
1
2
2
3
2
3

106

M. Aghazadeh et al. / Hydrometallurgy 111112 (2012) 103108

Table 4
ANOVA table for the quadratic model.
Source

Sum of
squares

Model
39.32
A
22.04
B
0.042
C
0.38
D
3.38
E
1.04
AB
0.063
AC
0.063
AD
3.06
AE
1.56
BC
0.56
BD
0.063
BE
0.063
CD
0.063
CE
0.063
DE
0.56
A2
1.79
B2
1.74
2
C
0.43
2
0.43
D
E2
1.74
Residual error
3.39
Lack of t
2.19
Pure error
1.20
Total
42.71
R-squared = 0.9207

DF

Mean
square

F-value

p-value

Remarks

20
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
10
6
4
30

1.97
22.04
0.042
0.38
3.38
1.04
0.063
0.063
3.06
1.56
0.56
0.063
0.063
0.063
0.063
0.56
1.79
1.74
0.43
0.43
1.74
0.34
0.36
0.30

5.81
65.08
0.12
1.11
9.97
3.08
0.18
0.18
9.04
4.61
1.66
0.18
0.18
0.18
0.18
1.66
5.27
5.13
1.27
1.27
5.13

0.003
b 0.0001
0.733
0.317
0.010
0.110
0.677
0.677
0.013
0.057
0.227
0.677
0.677
0.677
0.677
0.227
0.044
0.047
0.287
0.287
0.047

Signicant
Signicant

1.21

0.445

Signicant

Signicant

Signicant
Signicant

Signicant

of Variance (ANOVA) for the selected model is presented in Table 4.


The terms of the model with p-values less than 0.05 (corresponding
to 95% condence margin) are usually considered signicant. Moreover, signicant terms with higher F-values have a larger inuence
on the response. Therefore, the results of ANOVA suggest that surface
quality of copper deposits is primarily inuenced by Cu 2+ concentration (A), current density (D) and their interaction effect (AD). Moreover, Zn 2+ concentration (B) and the electrolyte temperature (E) are
moderately inuential parameters from their second order effects.
As seen in the table, non-signicant Lack of Fit conrms the adequacy of the quadratic model. The lack of t F-value of 1.21 implies
that it is not signicant relative to the pure error and there is a
44.5% chance that an F-value this large could occur due to noise.
The model adequacy can be further investigated by the examination

Fig. 3. Normal plot of residuals for DMI.

Fig. 4. Perturbation plot showing the effects of the main factors on the DMI for copper
cathodes.

of residuals, the most important of which is a check of the normality


assumption. Normal plot of residuals for DMI data is shown in Fig. 3.
The residuals appear to follow a straight line. Therefore, there is no
sign of any problem in the data and the model is statistically valid.
After discarding the insignicant terms from the quadratic model,
a rened model in the form of Eq. (2) is obtained, which predicts the
DMI of copper cathodes as a function of the inuential factors
expressed in the coded units.
DMI 2:030:96A 0:042B 0:37D0:21E
2

0:28A 0:22B 0:22E 0:44AD

Comparison of the regression coefcients in the model conrms


that the concentration of Cu 2+ in the electrolyte and cathodic current
density are the most inuential factors on. Perturbation plot for the
DMI of copper cathodes (Fig. 4) can be used to compare the effects
of all factors with reference to a particular point in the design space.
To make such plots, response values are plotted as a function of

Fig. 5. Interaction plot of Cu2+ concentration (A) and current density (D).

M. Aghazadeh et al. / Hydrometallurgy 111112 (2012) 103108

only one variable factor while other factors are kept constant at the
midpoint (level 0). Sensitivity of the response value to the variation
of the variable factor becomes evident from the slope or curvature intensity of the plot. A relatively at line is an indication that the response is almost insensitive to the variable factor. Steep slop of
curve (A) corresponding to Cu 2+ concentration shows that this factor
has the largest effect on the deposit morphology. It is also evident
from this curve that sensitivity of deposit layer smoothness to Cu 2+
concentration in the electrolyte becomes low at higher Cu 2+ concentrations. This is because of the presence of A 2 term in Eq. (2). At low
concentrations of Cu 2+, the rate of diffusion is presumably slow and
therefore, the cathodic process becomes diffusion-controlled. Under

107

such conditions powder formation is favored, since the rate of nucleation becomes much greater than the rate of crystal growth (Habashi,
1998). Fig. 5 shows the interaction effect of Cu 2+ concentration and
current density symbolized by AD in Eq. (2). It indicates that high
levels of cathodic current density (D) at low Cu 2+ concentrations
(A) cause the low quality deposits.
3.2. Optimization for DMI
Response surface methodology indicates areas in the design space
where the process is likely to give desirable responses. A simple mean
to nd the desired operating condition would be construction and

Fig. 6. Contour plots showing the effects of Cu2+ concentration (A) and cathodic current density (D) on the DMI at low, mid and high levels of Zn2+ concentration (B) and electrolyte temperature (E), and xed level of free H2SO4 concentration (C).

108

M. Aghazadeh et al. / Hydrometallurgy 111112 (2012) 103108

interpretation of contour plots. Fig. 6 exhibits the contour plots for


signicant Cu 2+ concentration (A) and cathodic current density (D)
factors on the DMI response variable at low, mid and high levels of
signicant Zn 2+ concentration (B) and electrolyte temperature (E)
factors and xed level of insignicant free H2SO4 concentration (C)
factor. From such plots, the optimum conditions for a dense and
smooth deposit can be deduced.
It is clearly seen from the plots that favorable condition for high
surface quality (smooth and compact) deposits, i.e. DMI = 1, generally
includes high Cu 2+ concentrations and high current densities (above
40 g/L and 250 A/m 2, respectively) regardless of the level of other experimental parameters. However, the area corresponding to the optimum condition extends to low current densities (down to 50 A/m 2)
and mid Cu 2+ concentrations (3040 g/L) when the electrolyte temperature is high (60 C). The existence of the second-order effect of
temperature that prevails over the interaction effect of Cu 2+ concentration and cathodic current density (terms 0.22E 2 and 0.44 AD
in Eq. (2), respectively) is responsible for this behavior. Ratio of cathodic current density to metal ion concentration in the electrolyte
has been known as a decisive factor that inuences the morphology
of deposits in the electrodeposition process of metals (Winand,
1992). High values of the ratio tend to favor the deposition of powders, because, as mentioned before, the rate of nucleation would be
much larger than the rate of crystal growth. The results of the present
investigation conform to this behavior.
Under the conditions of the present study, it is realized that it
would be possible to produce quality copper deposits despite very
high levels (40 g/L) of zinc in the electrolyte. Nevertheless, as mentioned earlier in this paper, there are different reports about the inuence of zinc ions on the microscopic morphology of the copper
cathodes. Gana et al. (1999) have reported that morphology of copper
deposits obtained by electrolytic recovery from CuSO4 solutions containing 1020 g/L Zn 2+ has been of a dendritic structure with dendrite
size increasing with Zn 2+ concentration in the electrolyte. However,
Muresan et al. (1999) have pointed out that the presence of
50500 mg/L of Zn 2+ had no effect either on the crystal growth orientation of the copper deposits or on their composition, while it slightly
changed the morphology by increasing the microscopic roughness.
Electrolytic recovery of copper from copper-zinc sulfate solutions
obtained by hydrometallurgical treatment of brass ashes and ue
dusts has been studied by Duman et al. (1989). It was revealed that
Zn 2+ ions cause grain size reductions of the cathodic copper in relatively high copper electrolytes. Presence of Zn 2+ also increased the
adhesion between the cathodic deposit and the substrate.
Although discussion on the purity of the obtained copper deposits
is beyond the scope of this paper, it is worth to mention that maximum zinc concentration in the cathodic copper deposit was less
than 200 ppm even for very high zinc concentrations in the electrolyte, while copper deposits with zinc contaminations of less than
about 1 ppm could be obtained under specic conditions.
4. Conclusions
Direct electrowinning of brass scrap, comprising a concurrent
electroleachingelectrodeposition process, has been introduced as a
potentially viable method for the selective recovery of copper. It has
the advantages of process simplicity, low energy costs and much
less environmental pollution as compared to the secondary smelting
operations. The present investigation was planned and performed to
verify the effects of the likely inuential process variables on the surface quality of copper cathodes obtained by direct electrowinning of a

7030 brass scrap, and to model and optimize the surface quality
using a CCD methodology. The main results achieved in the study
can be summarized as follow:
1) An inventive Deposit Morphological Index was employed to categorize the surface quality of copper cathode products with respect to
their apparent morphological features in an immediate and
straightforward manner. The index was employed as the response
variable for modeling and optimization.
2) Concentration of Cu 2+ in the electrolyte and cathodic current density was identied to be the most effective factors inuencing the
surface quality of copper cathodes.
3) Effects of the electrolyte temperature and Zn 2+ concentration
were found to be relatively small, while that of free H2SO4 concentration was essentially insignicant for the experimental objective
of this study.
4) Contour plots obtained from the quadratic model were employed
for optimization. It was found that high concentrations of Cu2+
(4050 g/L) together with high current densities (250350 A/m 2)
could generally produce a compact and smooth deposit irrespective
of the level of other factors. However, if the electrolyte temperature
is relatively high (about 60 C), low current densities and mid Cu2+
concentrations also could favor desirable deposits.
5) The presence of zinc ions in the electrolyte, even at very high concentrations of about 40 g/L, did not appreciably affect the surface
quality of copper deposits on the macroscopic level.
References
Alfantazi, A.M., Valic, D., 2003. A study of copper electrowinning parameters using a
statistically designed methodology. J. Appl. Electrochem. 33, 217225.
Dana, R.L., 1984. Sampling and Analysis in the Production and Consumption of Copper
Cathodes. In: Tuddenham, W.M., Hibbeln, R.J. (Eds.), Sampling and Analysis of Copper Cathodes (ASTM Special Technical Publication, STP-831). ASTM, pp. 715.
Davenport, W.G., King, M., Schlesinger, M., Biswas, A.K., 2002. Extractive Metallurgy of
Copper, 4th ed. Elsevier Science Ltd, Oxford, pp. 355365.
Duman, I., Bor, F.Y., Kammel, R., 1989. Researches on electrolytic deposition of copper
from copper and zinc sulphate solutions. Metallurgical 43, 142147.
Figueroa, M., Gana, R., Kattan, L., Parodi, A., 1994. Direct electrorening of copper scrap using
a titanium anode-support system in a monopolar cell. J. Appl. Electrochem. 24, 206211.
Figueroa, M., Gana, R., Kattan, L., Meandez, S., Palma, L., 1997. Anode-support system
for the direct electrorening of cement copper Part III: pretreatment and process
conditions to rene industrial cement. J. Appl. Electrochem. 27, 99103.
Gana, R., Figueroa, M., Kattan, L., Castro, S., 1993. Direct electrorening of copper scrap using
a titanium anode-support system in a bipolar cell. J. Appl. Electrochem. 23, 813818.
Gana, R., Figueroa, M., Kattan, L., Sanchez, J.M., 1995a. Anode-support system for the direct electrorening of cement copper Part I: process conditions using horizontal
rotary cathodes. J. Appl. Electrochem. 25, 240246.
Gana, R., Figueroa, M., Kattan, L., Moller, I., 1995b. Anode-support system for the direct
electrorening of cement copper Part II: process conditions using a circular cell
with vertical rotary cathode. J. Appl. Electrochem. 25, 10521056.
Gana, R., Figueroa, M., Kattan, L., Grandoso, D., Esteso, M.A., 1999. Analysis of the presence of different contaminants on the copper electrodeposits morphology
obtained from cement copper acid solutions. J. Appl. Electrochem. 29, 14751479.
Habashi, F., 1998. Principles of Extracive Metallurgy, Vol.4: Amalgam and Electrometallurgy, Metallurgie Extractive Quebec, p. 70.
Jackson, E., 1986. Hydrometallurgical Extraction and Reclamation. Ellis Horwood Limited, Chichester, p. 69.
Langer, S.H., 1975. Electrochemical Recovery of Copper from Alloy Scrap. US Patent No.
3959096.
Lazic, .R., 2004. Design of Experiments in Chemical Engineering. WILEY-VCH, Weinheim.
Lupi, C., Pilone, D., 1998. Experimental method for direct electrorening of both copper
and copper alloy scrap. In: Mishra, B. (Ed.), Proceedings of EPD Congress 1998.
TMS, pp. 427432.
Montgomery, D.C., 2001. Design and Analysis of Experiments, fth ed. John Wiley &
Sons, New York.
Muresan, L., Nicoara, A., Varvara, S., Maurin, G., 1999. Inuence of Zn2+ ions on copper
electrowinning from sulfate electrolytes. J. Appl. Electrochem. 29, 719727.
Winand, R., 1992. Electrocrystallization-theory and application. Hydrometallurgy 29,
567598.

Você também pode gostar