Materials Transactions, Vol. 46, No. 12 (2005) pp.

2719 to 2724
Special Issue on Growth of Ecomaterials as a Key to Eco-Society II
#2005 The Japan Institute of Metals

Removal of Lead from Copper Alloy Scraps by Compound-Separation Method

Atsushi Nakano1; * , Nurul Taufiqu Rochman2 and Hidekazu Sueyoshi1
1
Graduate School of Science and Engineering, Kagoshima University, Kagoshima 890-0065, Japan
2
Research Center for Physics, Indonesian Institute of Science, Tangerang 1530, Indonesia

Recently, the global scale environmental problem has become a critical issue. In metallic material, not only the cost reduction and
improvement of mechanical properties but also the decrease in environmental load is required. In copper alloys, several mass% Pb was added to
improve the machinability. However, due to the adverse toxicity of Pb that is harmful to the health, a new regulation to limit the amount of Pb
permitted in drinking water supplies has been enforced. A huge amount of copper alloy scraps containing Pb will become industrial waste
because the scrap will not be available as the raw materials.
We developed a new technique for removing Pb from copper alloy scraps in order to promote recycle of copper alloy scraps containing Pb.
Pb was removed from brass and bronze using compound-separation method.
Copper alloys containing 2–6 mass% Pb were molten using a high-frequency induction furnace under nitrogen atmosphere. Ca–Si
compound and NaF were added into the molten copper alloys to form large particles of a Pb compound. The large particles of the Pb compound
were skimmed off from the molten copper alloys. Liquid metal extractions and castings were characterized by electron probe microanalyser
(EPMA) and fluorescence X-ray (XRF) analysis.
The results show that high percentage (83% in brass and 82% in bronze) of Pb removal can be achieved. Therefore Pb-free copper alloys
can be produced from copper alloy scraps, resulting in the solution of environmental problems.

(Received June 2, 2005; Accepted November 10, 2005; Published December 15, 2005)
Keywords: lead removal, lead-free copper alloys, compound-separation method, recycle

1. Introduction which the floating large particles of a Pb compound were

Copper alloys (Brass and Bronze) containing several
mass% of Pb have been widely used in water faucets and
pipes for freshwater supply because of its good machinabil-
ity, corrosion resistance and mechanical properties. How-
ever, Pb is harmful to human health. In order to limit the
amount of permitted Pb in drinking water supplies the
regulations were enforced. The leaching standard value of Pb
was severely revised to 0.01 mg/L in Japan in April, 2003.1)
As a countermeasure, the development of the Pb-free copper
alloys has been advanced. Most of the developed Pb-free
copper alloys contain Bi as an alternative of Pb. However,
these Pb-free copper alloys are manufactured from the virgin
materials. This is caused by low technology for removing Pb
from the copper alloy scraps. If we continue the manufactur-
ing method only using virgin materials, the resource
consumption of not only Bi, which is the rare metal, but
also Cu, Zn and Sn increases. Also a huge amount of copper
alloy scraps containing Pb will be accumulated without being
recycled. These are not desirable from the viewpoints of
efficient use of resource and recycling.
In order to solve these issues, the development of the new
technology for removing Pb from the copper alloy scraps
containing Pb is needed. As the methods for Pb removal,
evaporation method using Cl and oxidation method have
been applied so far.2,3) However, these methods may not be
applied today because of their large environmental impacts
and long processing time. Authors have examined the
possibility of the Pb removal by compound-separation
method in brass.4–6)
In the present study, the compound-separation method in
skimmed off from the molten copper alloys was investigated
in both brass and bronze.
2. Experimental Procedure
Brass (JIS CAC203) containing 2.15 mass% Pb and bronze
(JIS CAC406) containing 5.5 mass% Pb were used as test
specimens. Table 1 shows the chemical composition of brass
and bronze. These specimens were observed by electron
probe microanalyzer (EPMA). Figure 1 shows SE images of
the brass and the bronze. The white spots in the SE images
indicate Pb, which remains undissolved within the matrix and
is dispersed as particles of several mm in size.
Figure 2 shows a schematic illustration of the experimen-
tal procedure. Brass (3 kg) and bronze (5 kg) were melted
using high-frequency induction furnace (20 kW) under nitro-
gen gas, respectively. Carbon crucible was used for melting
pot (Inner diameter: 110 mm, high: 250 mm). In order to form
Pb–Ca compounds, marketed Ca–Si compound was used.
Table 2 shows the chemical composition of the Ca–Si
compound. According to X-ray diffraction (XRD), this
compound consists of CaSi2 and Si. In the case of brass,
the Ca–Si compound was added to the molten brass at
1273 K. After agitating and holding, the formed large
particles of a Pb compound rose through the molten brass.
Such Pb compounds were then skimmed off from the molten
brass. We designate this process as ‘‘Stage I’’. After the
Stage I, an aggregation agent, NaF, was added to remove the
Table 1 Chemical composition of copper alloys used (mass%).

Cu Pb Sn P Fe Mn Al Si Zn
*Graduate Student, Kagoshima University. Present address: Graduate Brass 58.51 2.15 0.07 — 0.05 0.005 0.6 <0.005 38.58
School of Science and Engineering, Kagoshima University, Kagoshima
Bronze 83.11 5.50 4.56 0.011 0.28 <0.005 <0.005 <0.005 6.33
890-0065, Japan
2720 A. Nakano, N. T. Rochman and H. Sueyoshi

(a) (b)

10µm

Fig. 1 SE images of (a) as-received brass and (b) as-received bronze.

Brass Bronze

Melting Melting

Temperature setting Temperature setting

Agitation Agitation
Stage
Holding Ca-Si compound
Holding
Pb compound removal
Agitation
Stage Agitation
Holding
Sampling Holding NaF
Pb compound removal
Pb compound removal
Sampling
Casting Casting

Characterization Characterization
( XRF , EPMA ) ( XRF , EPMA )

Fig. 2 Schematic illustration of experimental procedure.

Table 2 Chemical composition of Ca–Si compound (mass%).
Ca Si Al Fe
28.8 61.0 1.48 5.1
remained small Pb compounds from the molten brass. We
designate this process as ‘‘Stage II’’.
When the Ca–Si compound was added to the molten
bronze, the percentage of Pb removal was about 20%. Bronze
contains Sn as shown in Table 1. Figure 3 shows standard
Gibbs energies (
G ) for synthesis of Ca2 Pb, Ca2 Sn, SnF2
and SnF4 as functions of temperature (Obtained by HSC
chemistry 5 in Outokumpu Research). It is suggested that Sn
reacts with F in preference to Ca though Ca reacts with Sn in
preference to Pb. Therefore, NaF was added to the molten
bronze to form the Sn–F compound, followed by adding the
Ca–Si compound at 1323 K. The large particles of the Pb
compound were skimmed off from the molten bronze. In the
above-mentioned processes, the amount of the Ca–Si com-
pound, the holding time of molten copper alloys and the Pb
C
compound removal temperature were changed. After the
experiments, quantitative analysis of Pb in the specimens was
0.64
carried out by X-ray fluorescence (XRF). The microstruc-
tures of brass and bronze specimens were characterized by
EPMA.
3. Result and Discussion
Figure 4 shows relationships between percentage of Pb
removal from brass at Stage I and bronze and the amount of
the Ca–Si compound. As shown in Fig. 4, the percentage of
Pb removal increases with increasing the amount of Ca–Si
compound. However, it tends to saturate with further
4 mass% additions in brass and 10 mass% additions in
bronze.
Figure 5 shows relationship between percentage of Pb
removal and holding time of molten brass. The percentage of
Pb removal increases abruptly with holding time until 10 min
and it saturates after 15 min. This suggests that Ca–Si
 Removal of Lead from Copper Alloy Scraps by Compound-Separation Method 2721

0 100

Brass ( Stage I )

Percentage of Pb removal (%)

Ca2 Pb 80
-200

Ca2 Sn
60
-1

-400
∆ G / kJ · mol

SnF2 40
0

-600
20

-800 0
SnF4 0 10 20 30
Holding time, t /min
-1000
773 973 1173 1373 1573 Fig. 5 Relationship between percentage of Pb removal and holding time.
(The amount of Ca–Si compound: 4 mass%, Pb compound removal
T/K temperature: 1158 K.)

Fig. 3 Comparison of Standard Gibbs energies for synthesis of Ca2 Pb,

Ca2 Sn, SnF2 and SnF4 .
100
Brass ( Stage I )
100 Bronze
Percentage of Pb removal (%)

80
Brass ( Stage I )

80 Bronze
Percentage of Pb removal (%)

60

60
40

40 20

20 0
1100 1150 1200 1250 1300

0 T/K
0 2 4 6
C cs / mass%
Fig. 4 Relationships between percentage of Pb removal and the amount of
Ca–Si compound, Ccs. (In brass, holding time: 15 min, Pb compound
removal temperature: 1220 K. In bronze, holding time: 13 min, Pb
compound removal temperature: 1183 K.)
compound reacts quickly with Pb, and then most of the
formed Pb compounds of solid phase move up to the surface
of molten brass in about 15 min.
Figure 6 shows relationships between percentage of Pb
removal and Pb compound removal temperature. In both
brass (Stage I) and bronze, the percentage of Pb removal
increases with decreasing Pb compound removal temper-
ature. But, in bronze, when Pb compound removal temper-
ature is lower than 1183 K, the percentage of Pb removal
decreases.
8 10 Fig. 6 Relationships between percentage of Pb removal and Pb compound
removal temperature. (In brass, the amount of Ca–Si compound: 4 mass%,
holding time: 15 min. In bronze, the amount of Ca–Si compound:
8 mass%, holding time: 13min.)
In 6 mass% Ca–Si compound addition to molten brass, the
state of retained Pb after Stage I was characterized by
EPMA. Figure 7 shows EPMA analysis of brass after
Stage I. The distribution of Pb is similar to that of Ca, and
Si exists around the Pb compounds. The particle size of Pb
compounds is very small. On the other hand, Ca–Si
compound particles which are unreactive to Pb are observed
in Fig. 7. This suggests that the added Ca–Si compound was
too much to Pb content in brass. In Fig. 4, when the amount
of Ca–Si compound exceeds 4 mass%, the percentage of Pb
removal saturates, which may be caused by the addition of
too much Ca–Si compound.
2722 A. Nakano, N. T. Rochman and H. Sueyoshi

Cu Zn Cu Sn

Ca Si Ca Si

Pb SE Pb SE

10µm 10µm

Fig. 7 EPMA analysis of brass after Stage I. (The amount of Ca–Si Fig. 9 EPMA analysis of bronze after Pb compound removal. (The amount
compound: 4 mass%, holding time: 15 min, Pb compound removal of Ca–Si compound: 8 mass%, holding time: 13 min, Pb compound
temperature: 1158 K.) removal temperature: 1183 K.)

Ca Si Pb Ca

Pb SE SE

10µm 10µm

Fig. 8 EPMA analysis of skimmed off compound from molten bronze. Fig. 11 EPMA analysis of brass after NaF addition (Stage II). (Condition
(The amount of Ca–Si compound: 8 mass%, holding time: 13 min, Pb of Stage I, the amount of Ca–Si compound: 4 mass%, holding time:
compound removal temperature: 1183 K.) 15 min, Pb compound removal temperature: 1158 K.)
 Removal of Lead from Copper Alloy Scraps by Compound-Separation Method 2723

Figure 8 shows EPMA analysis of skimmed off com- Pb content, C Pb / at %

pound from molten bronze. The distribution of Pb is similar
20 30 40 50 60 70 80 100
to that of Ca. This indicates that the Pb compound is formed. 1673
Si exists around the Pb compound. The Pb compound is very Brass
large (several ten mm). Such large particles of the Pb Bronze
compound may be moved up to the surface of molten 1473
bronze.

T/K
In 8 mass% Ca–Si compound addition to molten bronze, 1323K
Fig. 9 shows EPMA analysis of bronze after Pb compounds

Ca5 Pb 3
1273K

Ca2 Pb
1273
removal. The distribution of Pb is similar to that of Ca. This
1183K
indicates that Pb compounds are formed. The particle size of

Pb compounds is very small (several mm). Besides, the Ca–
Si compounds particles which are unreactive to Pb are not
seen in Fig. 9. The Pb concentration in as-received bronze is
2.5 times to that in as-received brass. Therefore, it is
considered that most of Ca–Si compound particle reacted
with Pb.
The above-mentioned results are discussed based on
equilibrium phase diagram of Ca–Pb system.7) Figure 10
shows equilibrium phase diagram of Ca–Pb system. We
assumed that every Ca reacts with Pb. When the 4 mass%
Ca–Si compound is added to molten brass, Pb concentration
in Ca–Pb componud becomes 65.1 mass%. When the 10
mass% Ca–Si compound is added to molten bronze, Pb
concentration in Ca–Pb compound becomes 65.6 mass%.
Ca–Si compound addition temperature is 1273 K in brass,
and 1323 K in bronze. According to the equiliblium phase
diagram, in both brass and bronze, both liquid phase and
solid phase (Ca2 Pb) coexist. The ratio of liquid phase in
bronze is larger than that in brass. After holding for a while
under such a condition, it is considered that adjacent liquid
phases coalesce to each other, and grow up to a large liquid
phase. When the temparature is lowered, the ratio of solid
phase increases. In other words, more solid phase is
crystallized in a liquid phase. Consequently, in both brass
and bronze, the amount of solid phase increases with the
decrease in temperature. Because large particles of the Pb
compound of solid phase becomes easier to move up to the
surface of molten copper alloys, the percentage of Pb
removal increases with decreasing Pb compound removal
temperature (Fig. 6). However, in bronze, when Pb com-
pound removal temperature is lower than 1183 K, percentage
of Pb removal decreases (Fig. 6). This is because the Pb
compounds of solid phase can not move up readily due to the
high viscosity of molten bronze at near solidification
temperature. Moreover, even when the Pb compound
removal temperature is the same in brass and bronze, the
percentage of Pb removal in brass is lower than that in
bronze. This suggests that it is for small Pb compounds of
solid phase difficult to move up to the surface of molten
brass. As shown in Fig. 4, in bronze, percentage of Pb
removal is 82% at 1183 K of Pb compound removal
temperature. According to the equilibrium phase diagram
(Fig. 10), not only solid phase but also liquid phase exists at
this temperature. This liquid phase remains in molten
bronze, because it is not possible to skim off from molten
bronze. As mentioned above, percentage of Pb removal in
brass was low because of small Pb compounds of solid phase
(Fig. 6). In order to aggregate these small Pb compounds,
NaF was added to molten brass after Stage I. As a result, the
CaPb
1158K
1073
50 60 70 80 90 100
Pb content, C Pb / mass %
Fig. 10 Equilibrium phase diagram of Ca–Pb system.
percentage of Pb removal was improved up to 83%.
Figure 11 shows EPMA analysis of brass after NaF
addition. Because small Pb compounds aggregate in molten
brass, the particle size of Pb compounds is very large (several
ten mm). These large Pb compounds may be moved up to the
surface of molten brass, resulting in the high percentage of Pb
removal. However, the upper limit of the percentage of Pb
removal is 83%. This is because liquid phase still remains as
shown in equilibrium Phase diagram.
The result of EPMA analysis showed that Na was absent in
brass and bronze ingots after Pb compound removal. A small
amount of Ca and Si remained in the ingots after Pb
compound removal. However, it is considered that the
residual Ca and Si may be removed by oxidation refining.
4. Conclusion
The method for removing Pb from copper alloys contain-
ing Pb was examined by the compound-separation method. In
the case of removing Pb from brass, Ca–Si compound is
added to molten brass, followed by skimming off the large Pb
compounds which float on the surface of molten brass. Then,
in order to aggregate the remaining small Pb compounds,
NaF is added to the molten brass. As a result, the large Pb
compounds are formed, resulting in the high percentage of Pb
removal. Using this method, 83% of Pb can, consequently, be
removed from brass containing 2.15 mass% Pb. In the case of
removing Pb from bronze, NaF is added to molten bronze,
followed by adding the Ca–Si compound. Therefore, the
reaction of Ca with Pb is promoted without the reaction of Ca
with Sn, resulting in the high percentage of Pb removal.
Using this method, 82% of Pb can be removed from bronze
containing 5.5 mass% Pb.
Acknowledgments
This work was supported by a Grant-in-Aid for Scientific
Research from Japan Society for the Promotion of Science,
No. 16510063.
2724 A. Nakano, N. T. Rochman and H. Sueyoshi
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