Paper 05-137(03).

pdf, Page 1 of 10
AFS Transactions 2005 American Foundry Society, Schaumburg, IL USA

Development of Lead-Free Copper-Nickel Alloys for

Food Processing Applications
M. Sadayappan, R. Zavadil, M. Sahoo
CANMET/MTL, Natural Resources Canada, Ottawa, Ontario, Canada
Copyright 2005 American Foundry Society

ABSTRACT
The lead in Cu-Ni alloy was replaced by bismuth and selenium. The role of lead in this family of alloys is to improve galling
resistance and machinability. The effects of bismuth and selenium on the mechanical properties, machinability and galling
resistance of the Cu-Ni alloy were evaluated. Even though it is possible to achieve comparable machinability and galling
resistance in lead-free alloys, the mechanical properties did not meet the specifications. The effects of bismuth and selenium
on the structure and properties of the alloy are presented and discussed in this publication.
INTRODUCTION
Copper alloys containing nickel, zinc, tin and lead, are a family of alloys known as nickel silvers. The most common alloy
C97600, also known as dairy metal, is widely used in food processing, architecture and marine applications. Alloy C97600
contains 3-5% lead which is added to improve machinability and galling resistance (Table 1). Concerns regarding lead
contamination in food could make these alloys unsuitable for the food processing industries. In order to preserve the market
(estimated to be about 20,000 tons/year) for the dairy metal, lead has to be replaced with other element(s). The most obvious
choice is a combination of bismuth and selenium in view of the earlier work done on the development of lead-free copper
alloys containing bismuth and selenium for drinking water applications (Whiting 1995, Sahoo 2000).
Table 1. Composition of Copper Alloy C97600 (Dairy Metal)

Range

Cu
63 - 67

Ni
19 21.5

Sn
3.5 4.5

Zn
3-9

Pb
3-5

Fe
1.5

Mn
1

Sb
0.25

Nominal

65

20.3

Other
0.08% S
0.05% P
0.15% Si
0.005% Al
-

To this end, MTL was approached by ASARCO to perform investigations to evaluate the mechanical properties,
machinability, grain refinement and galling resistance of Bi/Se modified nickel silvers and optimize the composition for
typical foundry operations. This project was undertaken to address some of the above issues and standardize the various
process parameters for the foundries to successfully produce these alloys.
BACKGROUND
The copper casting industry, as mentioned earlier, has successfully developed a family of copper alloys containing bismuth
and bismuth-selenium (EnviroBrass series) to replace leaded red brasses and yellow brass for plumbing applications in
response to concerns on lead contamination of drinking water. Following this trend, some nickel silver alloys containing
bismuth and bismuth-selenium were also developed but none of them are available in the open market and very little
information is available in the open literature. Few alloys, developed to have better galling and corrosion resistance, were
cited during a search of US patents (Sahu 2000, Venugpoalan 1998).
The information from earlier work to replace lead with Bi and Se in Cu-Ni alloys had indicated that the nickel content should
be restricted to 20% and a copper content of 64% would be ideal for the new lead-free alloy (Ojebuoboh, 2002). Iron and
manganese could be accommodated in small amounts, preferably less than 1%.

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AFS Transactions 2005 American Foundry Society, Schaumburg, IL USA

The major aim of this research was to make the designers aware of the importance of new lead-free Cu-Ni alloys. The
casting designers should be informed of these new alloys and their mechanical properties, machinability, corrosion resistance
and anti-galling characteristics. Similarly, the foundry operators should also be aware of the composition range and casting
characteristics of the alloy to cast the components for the food processing industry. The aim of this work was to develop
some data for designers.
EXPERIMENTAL DETAILS
COMPOSITION
Earlier work with Bi/Se modified red brasses indicated that the tin content should be preferably in the higher end of the range
to keep the bismuth in globular form. Also, the ranges for bismuth (1 to 3%) and selenium (1 to 2%) were selected to replace
4% of lead in the alloy. Zinc could be varied to make up the rest of the composition. The zinc content of the patented Bi-Se
modified Cu-Ni alloys reported in the patents varies between 2 and 6%.
The above rationale had resulted in the following composition: copper 64%, nickel 20%, tin 4 4.5%, zinc 7-9 %, bismuth 13%, and selenium 1-2%. In this investigation the iron and manganese were restricted to 1% and 0.5% respectively. It was
decided to prepare 10 alloys to investigate the effect of various alloy additions on the properties. A Design of Experiments
was carried out to identify test compositions.
Initially 500 kg of master alloy was prepared in an induction furnace. The composition of this alloy was Cu 21% Ni 4%
Sn 7% Zn 1% Fe - 0.3% Mn. Three samples were obtained for optical emission spectroscopy and wet chemical
analysis. This alloy was used in subsequent melts to maintain the same starting composition for all casting trials.
MELTING AND CASTING
Melting was carried out in a 110 kW, 3000 Hz push-up type induction furnace using coated clay graphite crucibles. Since CuNi alloy is prone to carbon pick-up from tools, only refractory coated steel tools were used during melting and handling. The
charge contained base alloy ingots, copper and Cu-10%Fe master alloy. The total charge per melt was 50kg. After melt
down, other alloy additions such as tin, bismuth, selenium and zinc were made. Pure bismuth, Bi-33% Se master alloy and
Cu-33% Se master alloy were used to get the desired bismuth and selenium levels. A sample was taken at this time to check
the composition in an optical emission spectroscope.
Trim additions were made to make-up the required composition. Cu-35% Mn master alloy was added just prior to
deoxidation which was achieved by adding 50 gm of magnesium and 100 gm of Cu-15% P master alloy. After deoxidation,
the crucible was taken out from the furnace at 1200C and poured into the molds. For comparison purposes, one alloy was
prepared with lead having composition close to C97600.
Three types of castings were produced in the experiment: keel block casting for tensile test specimens, ingot castings (1 x
3 x 12) for machinability test specimens and 1 cylinders for galling test samples. The keel block and cylinder molds were
prepared in CO2 sand. The machinability ingot was cast in a cast iron mold.
CHARACTERIZATION
Tensile properties of the alloys were evaluated using ASTM standard test bar having a gage diameter of 12.5 mm and a gage
length of 60 mm. The testing was carried out in an Instron machine and ultimate tensile strength (UTS), yield strength at
0.5% elongation and total elongation to failure were measured.
In case of machinability testing, the total energy and time consumed to drill a 12.5 mm diameter hole for a depth of 25mm in
a block was measured. These measures were rated against those for the free machining brass (C36000) which contains 3%
lead. The time and energy consumed for the free machining brass was rated as 100% and the test alloys were ranked
accordingly. Both leaded and lead-free dairy metals were tested.
Galling tests were performed in University of Windsor. Pin on disk configuration was used for the testing. The machine was
equipped with a loading arm enabling the tests up to a load of 1000 lb. The load range used was 400-1000 lb. The pin
material was 316-stainless steel (5mm diameter and 25mm height). The disk material was different Cu alloys (25mm
diameter and a 10mm height).
Sample surfaces were prepared with 600-grit SiC grinding paper and cleaned using acetone prior to each test. The tests were
performed according to procedures given in the ASTM standard G98. This method is used only as a qualitative test to
compare the performance of various new alloys. In this method, a selected load is applied and then one of the samples is
rotated (the disk in our case) for one revolution. Then, the sample surfaces are examined visually for galling.

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AFS Transactions 2005 American Foundry Society, Schaumburg, IL USA

RESULTS AND DISCUSSION

COMPOSITION
The composition of the alloys prepared was assessed using optical emission spectroscopy and wet chemical (Inductive
Coupled Plasma) analysis. The results are presented in Table 2 which includes one leaded Cu-Ni alloy prepared for
comparison purposes. The range of the elements is as follows: Ni: 18.3 20.5; Sn: 4 5.6; Zn: 6.3 8.8; Fe: 0.63 0.93;
Mn: 0.06 0.6. In case of bismuth the range was from 0.89 to 2.46% and selenium was varied between 0.9 and 2.37%.
These ranges for the elements were well within the initial experimental design.
Table 2. Composition of Alloys Prepared

Melt Trial Ni
3026 1
19.83
2
20.23
3027 1
19.56
2
19.35
3035 1
19.80
2
19.56
3050 1
20.50
2
20.30
3055 1
19.60
2
18.30
3110 1
19.60

Sn
3.99
4.01
3.97
4.25
3.85
4.53
4.00
4.40
3.94
5.61
4.31

Zn
7.77
6.32
6.68
6.27
6.66
7.07
8.80
7.90
7.15
6.70
6.09

Fe
0.82
0.72
0.88
0.93
0.67
0.58
0.53
0.54
0.70
0.61
0.60

Mn
0.39
0.06
0.33
0.34
0.45
0.43
0.50
0.49
0.60
0.61
0.54

Bi
0.89
1.02
2.40
1.90
1.57
1.09
1.04
1.22
2.46
2.29
0.00

Se Pb
1.05
2.13
1.00
0.90
2.37
2.22
0.91
0.94
1.11
1.13
0.00 5.25

MECHANICAL TESTING
The tensile properties of the alloys are presented in Table 3. The properties of the leaded alloy are also given along with the
specified minimum and typical values for alloy C97600 for comparison. The findings are as follows:
1. The tensile properties of lead-free alloys are always lower than that of the leaded alloy.
2. The ultimate tensile strength varies between 173 221 MPa and the range for the yield strength is between 172 and 219
MPa.
3. The ductility of lead-free alloys is less than 1% in most of the cases.
4. The properties could not be correlated with the bismuth or selenium contents.
5. The leaded alloy possess very high tensile strength (337 MPa) and yield strength (270 MPa) with 2.4% elongation. The
strength is much higher than the specified minimum for C97600 while the ductility is lower than the minimum of 10%.
One of the reasons for the low ductility may be the higher lead content in the alloy.
MACHINABILITY TEST
The results from the machinability tests, time and energy consumed for drilling a 12.5mm diameter hole for a depth of 25
mm, are presented in Table 4. The time and energy consumed by free machining brass was taken as 100 and the values for
all other alloys were rated against this standard. As seen from the table, the machinability of all the alloys tested in this
investigation was lower than that of the free machining brass.
The leaded dairy metal with 5.3% lead has a energy rating of 60 while the lead-free alloy with 2.46% Bi has 62 indicating
similar performance. The machinability of other lead-free alloys with lower amounts of bismuth, as measured by energy
rating, was much lower compared to even that of leaded alloy. The trend is similar when the rating for time is considered.
The results indicate that for lead-free alloys the machinability is controlled by the bismuth content and lower than the leaded
alloy. This is quite different from the red brasses where it was shown that Bi and Se acted synergistically improving the
machinability. In dairy metal, it is bismuth which contributes to the machinability.

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AFS Transactions 2005 American Foundry Society, Schaumburg, IL USA

Table 3. Mechanical Properties of Alloys Prepared

Melt
3026
3027
3035
3050
3055
3110
C97600

Trial
1
2
1
2
1
2
1
2
1
2
1
Min
Typical

UTS
210
173
192
190
184
198
221
221
184
217
337
276
310

YS Elong Bi
Se Pb
200 0.90 0.89 1.05
172 0.44 1.02 2.13
183 1.02 2.40 1.00
187 0.52 1.90 0.90
176 0.86 1.57 2.37
192 0.59 1.09 2.22
207 1.02 1.04 0.91
219 0.58 1.22 0.94
175 0.95 2.46 1.11
214 0.43 2.29 1.13
270 2.44 0.00 0.00 5.25
117 10
3
165 20
4

Table 4. Machinability Rating of Lead-Free Dairy Metal

Alloy

C36000
N3110-1
N3055-1
N3035-1
N3050-2
N3026-1

Consumed
Energy,
Time, s
joules
2040
22.00
3390
27.49
3269
32.10
4084
36.65
4380
37.61
5056
42.43

Rating, %
Energy
Time
100.0
60.1
62.4
49.9
46.5
40.3

100.0
80.0
68.5
60.0
58.5
51.8

Composition, %
Bi
Se
Pb
3
5.25
2.46
1.57
1.22
0.89

1.11
2.37
0.94
1.05

GALLING RESISTANCE
Five alloys were selected for evaluation of galling resistance (Table 5). They were selected for the difference in Bi and Se
contents. The leaded dairy metal was also tested for comparison.
Table 5. Composition of Alloys Tested for Galling Resistance

Melt Trial Ni
Sn Zn Fe Mn
3026
2
20.23 4.01 6.32 0.72 0.06
3035
1
19.80 3.85 6.66 0.67 0.45
3050
2
20.30 4.40 7.90 0.54 0.49
3055
2
18.30 5.61 6.70 0.61 0.61
3110
1
19.60 4.31 6.09 0.60 0.54

Bi
1.02
1.57
1.22
2.29
0.00

Se Pb
2.13
2.37
0.94
1.13
0.00 5.25

The results from the galling tests are presented in Table 6. The load at which the galling was observed is marked with an X
in the table. Galling was observed in the form of material transfer from the copper alloy discs to the stainless steel pin
surfaces. According to these results, the two alloys N3110 and N3055-2 seem to have similar galling resistances. N3110 is
the leaded alloy and N3055-2 is the lead-free alloy with the highest Bi content. Both of the alloys showed evidence of galling
at a load of 900 Lb. The other three alloys, where the bismuth content was less than 2%, the galling resistance was observed
very low. The incidence of the galling for these three alloys corresponded to loads of only 500-550 Lb. It is evident from the
above that for good galling resistance the dairy metal need at least 2% Bi in the place of nominal 4% lead present in the
leaded alloy. Selenium does not seem to be contributing to the galling resistance.

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AFS Transactions 2005 American Foundry Society, Schaumburg, IL USA

Table 6. Galling Test Results

Load (lb)
N3110
N3055-2
N3050-2
N3026-2
N3035
1000
damaged
900
X
X
800
X
X
X
9
9
700
X
X
X
9
9
600
X
X
X
9
9
550
X
X
X
9
9
500
X
9
9
9
9
400
9
9
9
9
9
Note - x refers to conditions where evidence for galling is observed

MICROSTRUCTURAL EVALUATION
The microstructures of the dairy metal with and without lead were investigated using optical and scanning electron
microscopes. Also, the fractured surfaces from lead-free alloys were examined to understand the failure mechanisms.
Leaded dairy metal
The structure of the leaded alloy, given in figure 1a. consists of primary phase dendrites with lead particles in the
interdendritic areas. A Cu-Ni-Sn rich phase is observed in the interdendritic areas, shown as gray patches in Figure 1b and at
a higher magnification image from SEM, Figure 1c.

a. 100 x

b. 500 x

c. 1600 x

Figure 1. Microstructures of leaded dairy metal, Melt N3110.

The constituents of the alloy were analyzed for the composition using energy dispersive x-ray analyzer (EDS). The results are
presented in Figure 2. The matrix is mostly copper with minor amounts of Ni, Sn and Zn and traces of Fe and Mn (Figure
2b). The gray particles are Cu-Ni-Sn intermetallics (Figure 2c) and have been observed in various shapes and sizes. The
large white particles observed in figure 2a are lead (Figure 2d).

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AFS Transactions 2005 American Foundry Society, Schaumburg, IL USA

a. BSE Image

b. Matrix, point 5

c. Gray particle, point 3

d. White particle, point 2

Figure 2. EDS analysis of phases in leaded dairy metal.

Lead-Free dairy metal

The lead free alloy contained bismuth and selenium as the replacements for lead. These elements were shown to be good
substitutes to achieve sufficient machinability in red brasses. The alloy consists of mostly primary dendrites and eutectics in
the interdendritic areas, as shown in the microstructure (Figure 3a). However, the volume fraction of the interdendritic
phases was not measured in this investigation, but much more than the eutectic phase observed in the leaded alloy
(comparing Figures 1a and 3a). This interdendritic phases in fact consist of particles of various composition as revealed by
their differences in color shown more clearly in Figure 3b and 3c.
One such cluster is shown in the secondary electron image in figure 4a. In this image various particles were identified and
their composition was analyzed using EDS. The EDS spectra for different phases are presented in Figure 4. The matrix
consist mainly of Cu, Ni, Sn and Zn and small amounts of Mn and Fe (Figure 4b), similar to the leaded alloy. Bismuth is
mostly observed independently with small amounts of Se (Figure 4c). Selenium is also observed in most of the gray
particles (4d and e).
The gray particles containing Cu, Ni, Sn and Se were widely distributed in the structure and are the prime reason for the
reduced properties of lead free alloys as revealed during the analysis of fractures from tensile testing. The fracture can easily
propagate through these particles.
The fractographs from the lead-free alloy, melt N 3026, are shown in Figure 5. The fracture is interdendritic in nature
(Figure 5a). At higher magnifications it is observed that the cracking is mostly along the particles in the interdendritic region
(Fig 5b). These particles are fractured in a brittle manner (Fig 5b) indicating the low ductility of the alloy. Even in the
matrix, fracture is propagating along the fine particles as shown in Figure 5c, which may be exposed due to debonding of the
matrix and particles.

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AFS Transactions 2005 American Foundry Society, Schaumburg, IL USA

a. Dendrites with Eutectic , 50X

b. Eutectic phase with particles, 200 X

c. Back scattered image showing the heavy particles (Bi appear white)

Figure 3. Microstructure of lead-free dairy metal, Melt N3055 1.

DISCUSSION
This investigation was aimed at removing lead from the dairy metal. Bismuth and selenium were used in combination as
possible replacements. The idea was extended from the previous development work on EnviroBrasses, the replacement for
leaded red brasses used in drinking water applications. However, in case of dairy metal the effects of these elements were
not similar. In EnviroBrasses, the influence of bismuth and selenium on the machinability is synergistic. This effect was
absent in dairy metal. Selenium formed intermetallic compounds with nickel along with copper and tin. This in turn
increased the amount of eutectic or other phases which were found to have segregated along the interdendritic and grain
boundary regions. This segregation contributed to easy crack propagation causing reduced mechanical properties including
poor ductility. Similarly, the machinability and galling resistance suffered by the absence of well distributed selenium
intermetallics in the matrix. In other words, selenium is not very useful in case of dairy metal. On the other hand, Sahu
(Sahu, 2000) reported that bismuth reduced the ductility of dairy metal when added alone, without the presence of selenium.
However, the effect of tin content was not studied in that alloy which may overcome the problem of low ductility. The effects
of these elements on the structure of nickel silvers should to be explored further.

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AFS Transactions 2005 American Foundry Society, Schaumburg, IL USA

a. BSE image

b. Matrix, position 8

c. Bi Particle, position 4

d. Gray particle, position 3

e. small gray particle, position 2, 5

Figure 4. EDS analysis of lead-free dairy metal, Melt N3027.

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AFS Transactions 2005 American Foundry Society, Schaumburg, IL USA

a. Fracture surface

b. Fracture along the particles

c. Particles in the matrix

Figure 5. Fractographs of lead-free dairy metal, Melt N3026.

CONCLUSIONS
1.
2.
3.
4.
5.
6.
7.

An effort was made to develop a lead-free dairy metal containing bismuth and selenium as the alloying elements in place
of lead.
Bismuth and selenium could be easily incorporated into the alloy without much melt loss.
The mechanical properties of lead-free alloys are less compared to those of the leaded alloys; especially the ductility is
significantly lower.
Machinability is found to be a factor of bismuth content alone. Selenium is not critical for machinability. It is possible to
achieve equivalent machinability in bismuth containing alloys to that of leaded alloys.
The galling resistance is also comparable to the leaded alloys. At least 2% Bi is required to achieve this levels of galling
resistance. Selenium does not contribute to the galling resistance.
The microstructural investigation indicates that selenium forms intermetallic compounds with other elements, such as Ni,
Cu and Sn. These particles are mostly observed in grain boundaries along with the eutectic.
Analysis of fracture surfaces indicated that these intermetallic particles contributed to the easier propagation of the
fracture and lower mechanical properties and ductility. This could also be the reason for the ineffectiveness of selenium
in improving machinability and galling resistance.

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ACKNOWLEDGMENT
The project was funded by Copper Development Association. The in-kind contribution from ASARCO and technical
assistance of Dr. Funsho Ojebuoboh, ASARCO is greatly appreciated. The help of staff of Casting Lab, ETS and Bob
Eagleson in casting, machining and mechanical testing is gratefully acknowledged. We wish to acknowledge Dr. Mustafa
Elmadagli of University of Windsor for galling resistance evaluation.
REFERENCES
Ojebuoboh, F., ASARCO, Private communication, 2002.
Sahoo, M., Sadayappan, M. and Fasoyinu, F.A., Permanent Mold Casting of Copper-Base Alloys for Plumbing
Applications, Journal of Korean Foundrymens Society, Vol 20, No.1, pp.3-12, 2000.
Sahu, S., Bismuthized Cu-Ni-Mn-Zn alloy, US Patent # 6.059,901, 2000.
Venugopalan, D., and Sahu, S., Selenized Se-Ni-Sn-Zn-Cu dairy metal, US Patent # 5,846,483, 1998.
Whiting, L.V., and Sahoo, M., "Modified Red Brass with Bismuth - A Literature Review and Analysis", AFS Transactions,
Vol. 103, pp.395-413, 1995.