May 2002

Materials Letters 54 (2002) 229 237

www.elsevier.com/locate/matlet

Preparation of shape-controlled copper oxide powders from

copper-containing solution
Younghee Ko Kim *, Doh-Hyung Riu, Soo-Ryong Kim, Byung-Ik Kim
Environmental Resource Laboratory, Korea Institute of Ceramic Engineering and Technology, 233-5 Gasan-Dong, Guemcheon-Gu,
Seoul 153-801, South Korea
Received 11 May 2001; received in revised form 6 August 2001; accepted 4 September 2001

Abstract
Shape-controlled copper oxides have been recovered from copper-containing waste etchant by neutralization with alkali
hydroxide. Large amounts of copper-containing waste etchant composed of copper chloride, hydrochloric acid and water are
generated from the printed circuit board (PCB) industry. In an environmental and economic point of view, the retrieval of the
valuable natural resource from waste is important. In the recycling process of copper oxide from the waste etchant, reaction
temperature controls the shapes and sizes of the products. Copper oxide recovered below the reaction temperature of 40 jC was
of the needle shape, while copper oxide comes in a platy shape above 40 jC. As a result of the experiments, more than 99% of
the copper in the waste etchant was recovered as copper oxide, and its by-products are only sodium chloride and water. Physical
properties of the samples have been characterized using scanning electron microscopy (SEM), X-ray powder diffraction (XRD),
thermal gravimetric analysis (TGA) and atomic absorption spectroscopy. The particle size scatters in the range of 0.5 10 Am.
Shape-controlled copper oxides are expected to be promising precursors for synthesizing copper powder by reduction. D 2002
Elsevier Science B.V. All rights reserved.
Keywords: Copper oxide; Copper-containing waste etchant; PCB industry; Sodium hydroxide; Neutralization

1. Introduction
Printed circuit boards (PCB) are widely used in
many electronic computer devices [1]. A chemical
milling process is commonly utilized in manufacturing printed circuit boards. In a typical chemical
milling process, an etchant solution etches the copper-plated printed circuit board. One of the most
common etchants in the electronic and computer

Corresponding author. Tel.: +82-2-3282-2472; fax: +82-23282-2430.

E-mail address: yhkokim@kicet.re.kr (Y.K. Kim).

industries is the acidic etchant which consists of

hydrochloric acid (HCl) and copper chloride (CuCl2).
The disposal of the etchant without proper treatment
has posed an environmental problem because the
acidic etchant contains a significant amount of copper (10 15 wt.%). In addition, the disposal of the
acidic etchant without treatment results in a great
economic loss. Recently, in an attempt to solve this
problem, there have been several approaches to recover copper from the etchant [2 4]. For example,
the copper oxychloride being used as an agricultural
ingredient is recovered by mixing the acidic etchant
with the alkali etchant that is also a waste from the
PCB industry.

0167-577X/02/$ - see front matter D 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 7 - 5 7 7 X ( 0 1 ) 0 0 5 6 8 - 7

230

Y.K. Kim et al. / Materials Letters 54 (2002) 229237

We attempted to develop a new process of recycling copper from an acidic etching solution such as
copper oxide. Copper oxide powder has been widely
utilized in many different fields such as a sintering
aid for ferrite compounds in the electronic industry,
an active constituent of fungicidal composition, a
catalyst and a pigment, etc. [5]. Various methods
are reported for the preparation of copper oxide [5].
Generally, copper oxide is produced by following
two processes. First, in pyrometallurgical process,
elemental copper is oxidized to copper oxide at 800
jC under oxygen atmosphere or air. Another common process for synthesizing copper oxide is the
neutralization process. Soluble salt of copper like
copper chloride, nitrate and carbonate is neutralized
with alkali hydroxide to produce copper oxide. The
waste etchant from the PCB industry contains quite a
large amount of copper chloride and is a good source
of soluble copper salt.
In this study, we report the preparation of highly
pure copper oxide from the acidic waste of the PCB
industry by neutralization with alkali hydroxide. This
process is a very environmentally benign process
where it generates only sodium chloride and water
as by-products. The recycled copper oxide has been
characterized using SEM, XRD, TGA and atomic
absorption spectroscopy.

2. Experiments
When the PCB is fabricated, waste etchant containing a large quantity of copper is produced during

Table 1
Physical properties of acidic and alkali etching solution from the
PCB industry
Components

Acidic etching
solution

Alkali etching
solution

Chemical

CuCl2+HCl+
H2 O
1.21 1.22

Cu(NH3)4Cl2+
NH4OH
1.21 1.23

10 15

10 15

Green
<1

Blue
> 14

Specific gravity
(25 jC)
Cu content
(wt.%)
Color
pH

Fig. 1. Block diagram of copper oxide synthesis.

the chemical milling process. The waste etchant can

be classified into two types: acidic waste etchant
(copper chloride waste etchant) and basic waste
etchant (alpine copper waste etchant). The physical
properties of the etching solution from the PCB
industry are given in Table 1. As shown in Table
1, the copper-containing etching solution that was
discharged in the PCB industry contains copper of
about 10 15 wt.% concentration.
For this study, the commercial etching solution,
waste etchant provided from the PCB factory, has
been used as a starting material for synthesizing
copper oxide. The process of copper oxide preparation from the acidic etching solution is available in
Fig. 1 as a block diagram. Sodium hydroxide solution of 33 50 wt.% is slowly added to the acidic
etching solution by maintaining the reaction temperature between 30 and 60 jC and then heated at 50 80
jC for aging. After several hours, the slurry is filtered and washed with water several times and sintered at 100 400 jC for 1 3 h.
It is recommended that 820 1100 g of 33 wt.%
sodium hydroxide solution is added to 1 l of the
acidic ething solution. If the sodium hydroxide added
is less than 820 g, the reaction is not complete, so its
product contains an excess of chlorine impurity.
Meanwhile, if the sodium hydroxide added is more
than 1100 g, an excess of sodium hydroxide is
unnecessarily consumed.

Y.K. Kim et al. / Materials Letters 54 (2002) 229237

The dried copper oxide is calcined at the preferable temperature of 100 400 jC. If the temperature
is lower than 100 jC, the calcination is not completely achieved. The dried copper oxide may be calcined
at a temperature of more than 400 jC, however, for
the sake of economical energy consumption, the
temperature of 400 jC at the maximum is most
desirable.
A Rigaku D/max-RINT 2500 diffractometer with
Cu Ka radiation was used for the XRD analysis of the
samples. Chemical analyses were performed by a
Jarrell-Ash Poliscan 61E inductively coupled plasma
(ICP) spectrometer and by a Perkin-Elmer 5000 atomic
absorption spectrophotometer. HITACHI S-4100 scanning electron microscope was used for the morphology
observation of the copper oxide precipitation. Particle
size distribution was measured using a particle size
analyzer (Beckman Coulter, Model LS 230). Thermogravimetric analyses were done using a Cahn TG
system 121 thermogravimetric analyzer. All samples
were heated to 700 jC at a rate of 10 jC/min under
nitrogen atmosphere.

231

3. Results and discussion

3.1. Neutralization of the acidic etchant with alkali
hydroxide
In the neutralization process, either sodium hydroxide or potassium hydroxide can be used as the
alkali aqueous solution. However, considering the
easiness of obtaining a material and a unit cost of
production of the copper oxide, it is preferred to use
sodium hydroxide.
By addition of the sodium hydroxide into the
acidic etchant below 40 jC, precipitation occurs.
Copper oxychloride (CuCl2
3Cu(OH)2) was formed
in the range of pH 5 8, and copper hydroxide
(Cu(OH)2) above pH 9. Fig. 2 shows the neutralization curve below 40 jC of the acidic etchant while it
neutralizes the sodium hydroxide solution. However,
with the addition of the sodium hydroxide into the
acidic etching solution above 40 jC, copper oxide
was formed in all pH ranges. Fig. 3 presents the X-ray
powder diffraction (XRD) patterns of copper oxides

Fig. 2. Neutralization curve of the acidic etchant.

232

Y.K. Kim et al. / Materials Letters 54 (2002) 229237

Fig. 3. X-ray powder diffraction patterns of copper oxides recovered from the copper-containing waste etchant.

recovered from the copper-containing waste etchant.

The sample was prepared at 30 jC to produce a copper hydroxide precursor and aged at 80 jC to get
copper oxide and dried at 100 jC. X-ray powder diffraction pattern is well matched with JCPDS No. 481548 without any impurities. However, the X-ray
powder diffraction pattern is quite broad. It is ascribed that the sample is not fully crystallized, a sintering process is required to get a highly crystallized
sample.

3.2. Effect of reaction temperature

Acidic etchants in the electronic and computer industries are composed of hydrochloric acid (HCl, 7
10%), copper chloride (CuCl2, 19 25.5%) and water
(H2O, 64.5 74%). The addition of NaOH to the
waste etchant generates large amounts of heat by
acid base titration since the waste etchant contains
a large amount of HCl. It leads to the instant increase
of reaction temperature of up to 80 jC. Copper oxide

Y.K. Kim et al. / Materials Letters 54 (2002) 229237

233

Fig. 4. Scanning electron microscopy analysis of copper oxides. (a) Reaction temperature: 60 jC. (b) Reaction temperature: 30 jC.

was formed at the beginning of the reaction. Prepared

copper oxide by this process shows a platy shape by
SEM analysis (Fig. 4a). On the other hand, the

addition of NaOH to the waste etchant while maintaining the reaction temperature under 40 jC leads to
the copper hydroxide slurry having a bright blue

Fig. 5. Particle size distribution of copper oxides. (a) Aging temperature: 50 jC. (b) Aging temperature: 80 jC.

234

Y.K. Kim et al. / Materials Letters 54 (2002) 229237

color. Aging of the copper hydroxide precursor at

50 80 jC for 1 3 h produces to black precipitation
of copper oxide. By SEM analysis, it can be seen that
the copper oxide prepared through the copper hydroxide precursor has a needle shape (Fig. 4b). The
process of needle shape formation of copper oxide
during the aging period was observed by scanning
electron microscopy (SEM). The SEM analysis shows
that the copper hydroxide precursor was of the junky
shape below 40 jC of reaction temperature. However,
needle-shaped copper oxides were grown from the
junky shape of the copper hydroxide 1 h after raising
the aging temperature to 80 jC, and for 3 h more, the
sample was completely turned into the needle-shaped

copper oxide. It is believed that copper oxide of the

needle shape was formed during the dehydration
stage of copper hydroxide. The high purity of fine
powder and the controllability of particle shape and
size are of importance for its practical use. It is
noted that the synthesis process plays an important
role in determining the shape and size of the
particles.
3.3. Effect of aging temperature
Aging of copper hydroxide precursor was performed at 50 80 jC for 1 3 h to increase the crystallinity of the final product of copper oxide. Particle

Fig. 6. Scanning electron microscopy analysis of copper oxides calcined at different temperatures (a) 100 jC, (b) 300 jC, (c) 400 jC and (d)
500 jC. The samples were prepared at 30 jC and aged at 80 jC.

Y.K. Kim et al. / Materials Letters 54 (2002) 229237

235

Fig. 7. Thermal gravimetric analysis data of copper oxides.

size distribution at different aging temperatures was

measured using the particle size analyzer. The average
particle size of copper oxides aged at 50 and 80 jC for

2 h was about 10 Am (Fig. 5). The aging temperatures

do not significantly affect the average particle size of
the copper oxide.

Fig. 8. X-ray powder diffraction patterns of copper oxides prepared at different conditions.

236

Sample
number

Reaction
temperature
(jC)

Aging
temperature
(jC)

Calcination
temperature
(jC)

Chemical analysis data

Cu2+
(wt.%)

Cu+
(wt.%)

Cl
(wt.%)

Na
(ppm)

M 22

30

80

M 20

40

80

M 23

50

80

M 19

60

60

300
400
500
300
400
500
300
400
500
300
400
500

78.3
78.6
78.1
78.7
79.1
80.2
78.8
78.7
79.4
78.9
79.4
80.5

2.28
2.3
2.16
Tr
0.74
0.62
1.26
1.50
1.23
Tr
1.65
1.31

Tr
Tr
Tr
Tr
Tr
Tr
Tr
Tr
Tr
Tr
Tr
Tr

Tr
Tr
Tr
Tr
Tr
Tr
Tr
Tr
Tr
Tr
Tr
Tr

Zn
(ppm)

Pb
(ppm)

Cd
(ppm)

Fe
(ppm)

28.24

40.94

<10

31.64

27.18

38.16

<10

31.81

28.52

40.57

<10

30.28

27.68

37.89

<10

27.54

Purity
as CuO
98.0
98.4
97.7
98.5
99.0
100.0
98.7
98.5
99.4
98.7
99.39
100.7

Y.K. Kim et al. / Materials Letters 54 (2002) 229237

Table 2
Chemical analysis data of the recovered copper oxides

Y.K. Kim et al. / Materials Letters 54 (2002) 229237

237

3.4. Effect of calcination temperature

Table 3
The result of shape-controlled copper oxide preparation

SEM analyses of calcinated copper oxide at different temperatures show different morphologies with
different calcination temperatures (Fig. 6). Sample
dried at 100 jC appears to have a long needle shape
having inhomogeneous particle size distribution.
However, the samples calcined at 400 or 500 jC
have spherical shapes and homogeneous size distributions. It is ascribed that recrystallization occurs at
the surface of the sample during the calcination
process.

Sample
number

Reaction
temperature (jC)

Aging
temperature
(jC)

Shape of final
products

M
M
M
M

30
40
50
60

80
80
80
60

Needle shape
Needle shape
Platy shape
Platy shape

3.5. Effect of reaction pH

4. Conclusion

The pH value (10.5 12) was controlled by the

amount of NaOH added while maintaining the reaction temperature under 30 jC. Each sample dried at
100 jC was analyzed using thermal gravimetric
analysis (TGA) (Fig. 7). Sample prepared at pH
10.5 shows weight loss at 300 jC. This weight loss
can be explained by the sublimation of chloride
impurity in the sample. However, the sample prepared
at pH 12 does not show significant weight loss at the
same temperature. TGA data confirm that the entire
chloride ions of the starting material are replaced by
hydroxyl ions only above pH 12. The above results
were also confirmed by X-ray powder diffraction
data. X-ray powder diffraction data of the sample
prepared at pH 12 show only copper oxide peaks.
However, X-ray powder diffraction data of the sample
prepared at pH 10.5 show copper oxychloride peaks
accounted for an impurity besides copper oxide peaks
(Fig. 8).

Highly pure copper oxides have been recovered

from copper-containing waste etchant of the PCB
industry. In recycling copper oxide from the waste
etchant by neutralization process using alkali hydroxide solution, the reaction temperature controls the
shapes and sizes of the copper oxides. The results
are summarized in Table 3. The copper oxide recovered below the reaction temperature of 40 jC was of
the needle shape, while copper oxide comes in a platy
shape above 40 jC. As a result of the study, more than
99% of the copper in the waste etchant was recovered
as copper oxide and its by-products are only sodium
chloride and water. Shape-controlled copper oxides
are expected to be promising precursors for synthesizing copper powder by reduction [6,7].

3.6. Chemical analysis and yield

The chemical analysis data of copper oxide prepared from waste etchant are shown in Table 2. The
purity and yield of copper oxide prepared from waste
etchant of the PCB industry are higher than 99%. It
contains impurities of Zn, Pb and Fe in ppm level.
Yield of recovered copper oxide was calculated
based on the copper concentration of the starting

22
20
23
19

material which is the commercial acidic etching

solution.

References
[1] G.R. Allardyce, A.J. Davies, D.J. Wayness, A. Singh, US Patent
5,106,454 (1992).
[2] M.A. Rabah, Hydrometallurgy 56 (2000) 75.
[3] B. Greenberg, US Patent 5,188,703 (1993).
[4] K.S. Doh, N.Y. Kim, D.K. Kim, J. Korea Solid Wastes Eng.
Soc. 14 (7) (1997) 667.
[5] H.W. Richardson, Hand Book of Copper Compounds and Applications, Marcel Dekker, New York, USA, 1997.
[6] L. Liu, T.J. Zhang, K. Cui, Y.D. Dong, J. Mater. Res. 14 (10)
(1999) 4062.
[7] J. Durisin, M. Orolinova, K. Durisinova, V. Katana, J. Mater.
Sci. Lett. 13 (1994) 688.