# Patent

## Title
Copper alloy water supply member

## Abstract

A member for water works is proposed in which the content of lead is limited to a very small values while maintaining its mechanical properties, castability, machinability, pressure resistance, etc. to levels equivalent to those of conventional copper alloys containing lead.
A copper alloy is produced which contains not less than 2.0% by weight and not more than 5.9% by weight of tin, not less than 1.5% by weight and not more than 5.0% by weight of nickel, not less than 5.0% by weight and not more than 12.1% by weight of zinc, not less than 0.4% by weight and not more than 3.3% by weight of bismuth, and not less than 0.009% by weight and not more than 0.15% by weight of phosphorus, the balance being copper and impurities.

## Background
TECHNICAL FIELD
This invention relates to a copper alloy material for members used in water works applications which leaches lead by an amount that is lower than a predetermined value.
BACKGROUND ART
Cast copper alloy ingot CAC406, which has heretofore been used for parts of water supply systems and devices, contain 4.0 to 6.0% by weight of lead. Thus, lead in this material tends to dissolve into tap water. In order to reduce the amount of toxic lead that dissolves into tap water, consideration is now being given to developing lead-reduced or lead-free copper alloys.
But such lead-reduced or lead-free copper alloys are difficult to cast and cut, and also tend to be low in pressure resistance. Valves made of such alloys therefore tend to cause water leakage. Alloys are thus being considered that are not only low in lead content, but sufficiently high in pressure resistance and other necessary properties compared to alloys that are higher in lead content.
Among such alloys is one disclosed in Patent document 1, to which bismuth and selenium are added to improve machinability. Patent document 2 discloses an alloy to which silicon and magnesium are added to improve strength and leaching properties.
[Patent document 1] JP Patent publication 2004-68096A
[Patent document 2] JP patent publication 2004-52106A
DISCLOSURE OF THE INVENTION
Object of the Invention
But because selenium also has some toxicities, the use of the alloy disclosed in Patent document 1, which contains selenium, as members for water works may have some harmful effects. An alloy containing silicon develops wool-like silicate, thereby promoting the formation of microporosity, which can in turn reduce the pressure resistance. Magnesium tends to form oxides such as magnesium oxide, which tend to be dispersed in the material, thereby lowing its elongation and considerably impairing its flowability.
On the other hand, in order to answer the global requirement for effective use of resources, efforts are being made to use recycled materials for more effective use of metallic resources. But recycled materials derived from conventional metallic products inevitably contain impurities including lead (though its content may be very small), because lead is generally used in such conventional metallic products. Alloys made of such recycled materials may therefore also inevitably contain trace amounts of lead.
An object of the present invention is therefore to provide a member for water works in which the content of lead and the amounts of metals that dissolve into water are limited to very small values, while maintaining its mechanical properties, castability, machinability, pressure resistance, etc. to levels equivalent to those of conventional copper alloys containing lead.
Means to Achieve the Object
To achieve the above object, the present invention provides a member for water works made of a copper alloy containing not less than 2.0% by weight and not more than 5.9% by weight of tin, not less than 1.5% by weight and not more than 5.0% by weight of nickel, not less than 5.0% by weight and not more than 12.1% by weight of zinc, not less than 0.4% by weight and not more than 3.3% by weight of bismuth, and not less than 0.009% by weight and not more than 0.15% by weight of phosphorus, the balance being copper and impurities.
ADVANTAGES OF THE INVENTION
The lead content of the copper alloy for the member used in water works applications according to the present invention is substantially equal to the content of lead contained as impurities in a recycled material used as a raw material. Thus, it is possible to minimize the amount of lead that dissolves into water. By adding predetermined amounts of tin, nickel, zinc, phosphorus and bismuth, the copper alloy can maintain sufficient castability, mechanical properties, pressure resistance, leaching properties and machinability even though the lead content is low, so that the copper alloy according to the invention can be advantageously used for members used in water works applications.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1(a) shows the shape of a spiral frame used in a test for flowability of molten metal for examples, and FIG. 1(b) is a sectional view taken along line A-A, of the spiral frame shown in FIG. 1(a).
FIG. 2 is a graph showing the reference straight line by a reference material in the test for flowability of molten metal, and data on other examples.
FIG. 3 shows a stepped mold which is less influenced by the feeding effect.
In FIG. 4(a), photos of sections of each stepped specimen show results of a liquid penetrant testing.
In FIG. 4(b), photos of sections of each stepped specimen show results of a liquid penetrant testing.
In FIG. 4(c), photos of sections of each stepped specimen show results of a liquid penetrant testing.
In FIG. 4(d), photos of sections of each stepped specimen show results of a liquid penetrant testing.
In FIG. 4(e), photos of sections of each stepped specimen show results of a liquid penetrant testing.
FIG. 5 is a table showing a decision method according to the shapes of powder chips in a test for machinability.
In FIG. 6(a), photos show the shapes of powder chips produced from Examples of the invention and Comparative Examples in a test for machinability.
In FIG. 6(b), photos show the shapes of powder chips produced from Examples of the invention and Comparative Examples in a test for machinability.
In FIG. 6(c), photos show the shapes of powder chips produced from Examples of the invention and Comparative Examples in a test for machinability.
In FIG. 6(d), photos show the shapes of powder chips produced from Examples of the invention and Comparative Examples in a test for machinability.
In FIG. 6(e), photos show the shapes of powder chips produced from Examples of the invention and Comparative Examples in a test for machinability.
In FIG. 7(a), photos show the results of mapping analysis by EPMA.
In FIG. 7(b), photos show the results of mapping analysis by EPMA.
In FIG. 7(c), photos show the results of mapping analysis by EPMA.
In FIG. 7(d), photos show the results of mapping analysis by EPMA.
In FIG. 7(e), photos show the results of mapping analysis by EPMA.
In FIG. 7(f), photos show the results of mapping analysis by EPMA.
In FIG. 7(g), photos show the results of mapping analysis by EPMA.
In FIG. 7(h), photos show the results of mapping analysis by EPMA.
In FIG. 7(i), photos show the results of mapping analysis by EPMA.



BEST MODE FOR EMBODYING THE INVENTION
The present invention is now described in detail.
This invention is directed to a copper alloy member for use in water works applications made of a copper alloy containing predetermined amounts of tin, nickel, zinc, bismuth and phosphorus, the balance being copper and impurities. The contents of lead and silicon contained in the impurities are lower than predetermined values. Description is first made of the respective elements forming the copper alloy for the member for water works according to the present invention.
It is essential that this copper alloy contains tin by not less than 2.0% by weight. Preferably, the tin content is not less than 2.4% by weight. The higher the tin content, the higher the tensile strength of the copper alloy, and the lower the elongation. Thus, if the tin content is less than 2.0% by weight, it may be difficult to obtain stable tensile strength. On the other hand, the tin content has to be not more than 5.9% by weight. Preferably, the tin content is not less than 5.2% by weight. If the tin content is higher than 5.9% by weight, the elongation of the copper alloy may be too low. As used herein, the mechanical properties refer to tensile strength and elongation. Here, good mechanical properties mean a high tensile strength and a high elongation.
The content of nickel in the copper alloy has to be not less than 1.5% by weight, and is preferably not less than 2.0% by weight. If the nickel content is less than 1.5% by weight, the copper alloy tends to develop casting defects and microporosity, which may in turn cause an unignorable increase in leaching of one or some elements. On the other hand, the nickel content has to be not more than 5.0% by weight and is preferably not more than 4.1% by weight. If the nickel content is higher than 5.0% by weight, the elongation will be too low. Because nickel shows a complete solubility in the solid state in copper as the main component, and its crystalline structure comprises a face-centered cubic lattice as with copper, nickel is a suitable element as one of the two substrate bases. Also, nickel serves to effectively reduce the tin concentration of the liquid phase at the solid-liquid interface during solidification, thus preventing segregation, and reducing casting defects, thereby improving pressure resistance. Nickel further forms compounds with tin and phosphorus in dendrite gaps, thereby filling microporosity. The compounds also serve as chip breakers to break chips into finely sheared powder.
The content of zinc in the copper alloy has to be not less than 5.0% by weight, and is preferably not less than 6.0% by weight. Also, the zinc content has to be not more than 12.1% by weight, and is preferably not more than 10.1% by weight. Zinc has a deoxidizing function, improves flowability of molten metal, and stabilizes the mechanical properties. By adding zinc by an amount between the abovementioned upper and lower limits, the strength of the copper alloy is substantially unchanged, so that zinc has no substantial influence on the mechanical properties. But if the zinc content is less than 5.0% by weight, flowability of the copper alloy in a molten state tends to be insufficient, and also, the copper alloy may develop microporosity. On the other hand, if the zinc content is higher than 12.1% by weight, the elongation will unignorably decrease. Also, during manufacturing, zinc skim may increase casting defects. Further, if the leaching of zinc exceeds a reference leaching value of zinc, the possibility of dezincification corrosion increases, and also, it becomes impossible to use such a copper alloy as a member for water works.
The content of bismuth in the copper alloy has to be not less than 0.4% by weight and also has to be not more than 3.3% by weight. The bismuth content is preferably not more than 2.0% by weight. Since bismuth is not soluble in a solid state in a matrix in a practical range and is present at grain boundaries and in crystal grains, it prevents development of casting defects in a solid state, which are peculiar to bronze castings. Also, bismuth in the alloy improves machinability. If the bismuth content is less than 0.4% by weight, these effects may not be obtained sufficiently. On the other hand, with an increase in the bismuth content, the elongation tends to decrease, though the tensile strength does not decrease. Therefore, if the bismuth content is higher than 2.0% by weight, the elongation tends to be low, so that the microporosity tends to develop. If the bismuth content exceeds 3.3% by weight, the elongation decreases to such an extent that the development of microporosity is unignorable.
If the tin content is not less than 5.1% by weight and not more than 5.2% by weight, even if the bismuth content is higher than 2.0% by weight, reduction in elongation and development of microporosity are relatively suppressed. But if the tin content is lower than the above range, these weak points tend to appear. Thus, in order to suppress these weak points with the tin content within the range of not less than 2.0% by weight and not more than 6.0% by weight, the bismuth content is preferably in the range of not less than 0.4% by weight and not more than 2.0% by weight.
The content of phosphorus in the copper alloy has to be not less than 0.009% by weight, and is preferably not less than 0.014% by weight. On the other hand, the phosphorus content has to be not more than 0.15% by weight, and is preferably not more than 0.10% by weight. Phosphorus acts as a deoxidizing agent during melting and casting, thereby improving flowability of molten metal during casting, and also improving healthiness of castings. If its content is less than 0.009% by weight, these effects are not obtained sufficiently, so that casting defects tend to develop. If its content is higher than 0.15% by weight, phosphorus tends to react with water in the mold, thereby increasing the possibility of casting defects.
In the alloy according to the present invention, the area ratio of nickel-tin and nickel-phosphorus compounds to the section of the material is preferably not less than 0.04%. If this area ratio is less than 0.04%, these compounds may not sufficiently fill gaps around these compounds which fill microporosity. On the other hand, this area ratio is preferably not more than 1.95%. If this area ratio is higher than 1.95%, the nickel compounds not only fill gaps, the physical properties of the nickel compound itself may have unignorable influences on the entire alloy.
The sum of the area ratios of bismuth and the above nickel compounds that appear on a section of the alloy is preferably not less than 0.72%. If this value is less than 0.72%, microporosity may not be filled sufficiently. On the other hand, this value is preferably not more than 5.95%. If this value is over 5.95%, the physical properties of these substances will have unignorable influences on the entire alloy.
The copper alloy may contain impurities other than the abovementioned substances and copper. Such impurities are substances that are inevitably contained in the copper alloy if e.g. recycled materials are used in producing the copper alloy for environmental consciousness. The content of such impurities should of course be as low as possible. The impurities include e.g. lead and silicon.
The content of lead in the copper alloy is preferably not more than 0.2% by weight, and should be as low as possible within the range of not more than 0.2% by weight. Lead has a large evil influence on the human body. Thus, in using the copper alloy for the member for water works according to this invention, it is necessary to minimize the amount of lead that dissolves into tap water. If this amount is higher than 0.2% by weight, it is difficult to meet the leaching standard value by the leaching test method under JWWA Z 108. Also, if the lead content is too large, the tensile strength and elongation may decrease excessively, or casting defects may develop. The lead content is, most ideally, zero. But as long as the copper alloy is made of recycled materials for efficient use of resources, it is not practical to reduce the lead content to zero.
The content of silicon in the copper alloy is preferably less than 0.01% by weight. While silicon serves to improve flowability of the copper alloy in a molten state, it develops wool-like silicon oxide when solidifying, thereby making it difficult to replenish molten metals and also increases the concentration of tin in the liquid phase at the solid-liquid interface. This helps the development of many microscopic casting defects between dendrites or at grain boundaries, which in turn results in water leakage. Silicon also considerably reduces the elongation of the copper alloy. If the silicon content is higher than 0.01% by weight, these detrimental effects tend to be unignorable. Thus, the silicon content should be as low as possible. But by limiting the silicon content to less than 0.01% by weight, these detrimental effects scarcely appear.
The abovementioned contents in weight of the respective substances are not the contents at the production stage, but the contents of the respective substances in the alloy obtained by melting the respective substances.
Ordinarily, since bronze castings have a wide solidifying temperature range, they solidify in the mushy type. Bronze castings that do not contain lead tend to develop microscopic shrinkage cavities between dendrites. This lowers the pressure resistance of members for water works that are made of such materials, thereby increasing the possibility of water leakage. Especially if such a member has a thick wall, this tendency is prominent due to a slow cooling speed during casting. On the other hand, in the case of a copper alloy containing a large amount of lead, lead collects between dendrites, thus reducing microporosity. According to the present invention, bismuth and nickel-tin and nickel-phosphorus compounds in the copper alloy play this role of lead. By adding predetermined amounts of nickel and bismuth, it is possible to reduce fine microporosity that tends to develop in the central portion with respect to the wall thickness direction. By adding a predetermined amount of phosphorus, phosphorus reacts with oxygen in the molten metal, which can cause gas defects, forming P2O5, thereby improving the soundness of the molten metal, and reducing microporosity. But if the silicon content is too high, casting defects tend to increase to such an extent as not to be curable by adding e.g. nickel.
The balance of this copper alloy is copper. The alloy containing the abovementioned elements can be produced by a method for producing ordinary copper alloys. The copper alloy member for water works made of this copper alloy can be manufactured by an ordinary casting method. For example, it can be manufactured by melting the alloy in a high-frequency induction furnace.
The copper alloy member for water works according to the present invention is made of an copper alloy that contains lead only in an amount substantially equal to the amount of impurities, and is characterized by good flowability of molten metal, high mechanical properties, fewer casting defects, high leaching properties and machinability, etc., compared to copper alloys containing larger amounts of lead. Thus, the member for water works made of this copper alloy is low in leaching amount of lead, and high in machinability, pressure resistance, etc.
Specifically, when compared with conventional CAC406 alloy, the machinability coefficient of the copper alloy according to the invention is at least 70 or higher. This value can be further increased according to the mixture ratio of the substances.
The machinability coefficient was calculated from three stress values that act on a cutting tool, i.e. circumferential force P1, force P2 in the feed direction and force P3 in the axial direction of the tool, which were measured by a dynamometer AST-TTH for type AST cutting tools made by Sato Kogyo Co., Ltd., and three stress values measured in the same manner for Comparative Material CAC406, according to the below equation (1). The “Resultant of three forces” in equation (1) is calculated according to equation (2) below.

(Machinability coefficient)=(Resultant of three forces for Comparative Material)/(Resultant of three forces for each material)×100  (1)

(Resultant of three forces)={(Circumferential force)2+(Force in the feed direction)2+(Force in the axial direction)2}1/2  (2)

In examples of the invention, when the cutting speed was 100 to 400 m/min., the depth of cut was 1.0 mm, and the feed rate was 0.1 mm/rev., the surface roughness was 0.6 to 1.1 μm. Under the same conditions, the surface roughness of CAC406 was 0.8 to 1.0 μm. Thus the surface roughness values are substantially equal to each other. The smaller the surface roughness value becomes, the smoother the surface becomes. Thus, the surface roughness value should be as small as possible.
Besides satisfying these values, chips are in the shape of spirals, broken powders, or sheared chips. Thus, no straight, helical or tubular chips are produced.
The flowability of the molten copper alloy according to the present invention is preferably such that it is equivalent to or higher than the flowability of conventional lead-containing copper alloys when the casting temperature is higher than the conventional temperature within the ordinary temperature range. More preferably, its flowability is equivalent or higher than the flowability of conventional lead-containing copper alloys at the same temperature as the conventional temperature. The casting temperature at which such flowability is achieved is preferably in the range of 1100 to 1200° C.
For the mechanical properties of the copper alloy according to this invention, the tensile strength and the elongation as measured under JIS Z 2241 are preferably equivalent or higher than those of CAC406 as a conventional lead-containing copper alloy. Specifically, the tensile strength is preferably not less than 195 MPa, and the elongation is preferably not less than 15%.
For casting defects, in a liquid penetrant testing under JIS Z 2343, no pattern indicative of defects appeared in the central portion in the wall thickness direction. Thus, production can be made by the same casting method as used for the conventional lead-containing copper alloy CAC406.
For the leaching properties or the like, too, in a leaching test method under JWWA Z 108 and in a leaching analysis method under JWWA Z 110, the lead concentration was not more than 0.1 mg/l, the zinc concentration was not more than 10 mg/l, the copper concentration was not more than 0.1 mg/l, and the cadmium concentration was not more than 0.001 mg/l. These values all satisfy the required standard values. Also, the lead concentration and the cadmium concentration are lower than 0.38 mg/l and 0.0004 mg/l, which are leaching amounts of lead and cadmium from CAC406, respectively. The copper alloy according to this invention is thus safer than conventional lead-containing copper alloys.
Copper alloy members for water works that are made of the copper alloy according to the present invention include water supply parts and instruments used in water supply facilities and devices, and other parts and instruments in which the use of lead is not desirable. Specifically, such members include pipes, valve bodies and bearings used in such valves as gate valves, repair valves, check valves, ball valves, solenoid valves, water stop valves, saddle valves and draft tube valves, case bodies of water meters, pipe couplings, faucet fittings and pump parts.
EXAMPLES
Examples are now shown to more specifically describe the invention. Respective materials were mixed together, and the mixtures were melted in a high-frequency induction furnace and cast in a CO2 die to prepare test specimens for the respective examples. Comparative Example 1 was prepared using as a reference material a conventional lead-containing bronze material CAC406 to compare physical properties. These prepared copper alloys were subjected to the below-described tests.














TABLE 1









Example 1
Example 2
Example 3
Example 4
Example 5




Comparative
of the
of the
of the
of the
of the
Comparative



Example 2
invention
invention
invention
invention
invention
Example 1





Element


Ni
2.5
2.5
2.5
2.5
2.5
2.6
0.2


Sn
2.5
2.7
2.7
2.5
2.6
2.4
5.8


Zn
4.1
5.1
6.0
8.4
10.1
12.1
5.1


Bi
0.5
0.6
0.6
0.6
0.5
0.5
—


P
0.017
0.022
0.017
0.019
0.015
0.023
0.021


Si
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
—


Pb
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
5.4


Cu
Balance
Balance
Balance
Balance
Balance
Balance
Balance


Flowability
X
Δ
Δ
Δ
◯
◯
Reference


of molten


metal


Mechanical
◯
◯
◯
◯
◯
◯


properties


Tensile
274
246
259
253
248
232
≧195


strength


Elongation
34.8
27.8
31.2
33.9
34.7
31.1
≧15


Liquid
X
Δ
◯
◯
◯
◯
Reference


penetrant


testing


Leaching
◯
◯
◯
◯
◯
◯
X


Machinability
71.2
77.9
72.7
—
80.8
81.3
100


coefficient


Surface
0.8
0.8
0.8
—
0.9
1.0
0.8


roughness


Shape of
◯
◯
◯
—
◯
◯
◯


chips


Evaluation of
◯
◯
◯
—
◯
◯
Reference


Machinability


General
X
Δ
Δ
Δ
◯
◯


















Example 6
Example 7
Example 8
Example 9




Comparative
of the
of the
of the
of the
Comparative



Example 3
invention
invention
invention
invention
Example 4





Element


Ni
2.5
2.5
2.5
2.5
2.5
2.5


Sn
5.0
5.4
5.2
5.2
5.1
5.3


Zn
3.9
5.0
6.0
8.1
9.7
12.4


Bi
0.5
0.5
0.6
0.6
0.5
0.5


P
0.016
0.021
0.015
0.022
0.020
0.027


Si
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01


Pb
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001


Cu
Balance
Balance
Balance
Balance
Balance
Balance


Flowability
X
Δ
Δ
◯
◯
◯


of molten


metal


Mechanical
◯
◯
◯
◯
◯
X


properties


Tensile
289
293
273
273
251
207


strength


Elongation
32.9
31.4
26.8
28.0
24.1
14.1


Liquid
X
Δ
Δ
Δ
Δ
◯


penetrant


testing


Leaching
◯
◯
◯
◯
◯
◯


Machinability
73.5
75.2
76.7
—
79.1
78.5


coefficient


Surface
0.9
0.9
0.9
—
1.1
0.9


roughness


Shape of
◯
◯
◯
—
◯
◯


chips


Evaluation of
◯
◯
◯
—
◯
◯


Machinability


General
X
Δ
Δ
Δ
Δ
X
























TABLE 2










Example
Example
Example
Example
Example




Comparative
Comparative
10 of the
11 of the
2 of the
12 of the
13 of the
Comparative



Example 5
Example 6
invention
invention
invention
invention
invention
Example 7





Element


Ni
0.0
1.0
1.5
2.0
2.5
4.1
5.0
6.0


Sn
2.6
2.6
2.7
2.3
2.7
2.4
2.4
2.4


Zn
6.0
6.0
6.9
6.8
6.0
7.1
7.2
7.3


Bi
0.5
0.5
0.5
0.4
0.6
0.5
0.5
0.5


P
0.006
0.007
0.020
0.016
0.017
0.019
0.016
0.025


Si
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01


Pb
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001


Cu
Balance
Balance
Balance
Balance
Balance
Balance
Balance
Balance


Flowability of
Δ
Δ
Δ
Δ
Δ
Δ
Δ
Δ


molten metal


Mechanical
◯
◯
◯
◯
◯
◯
◯
X


properties


Tensile
215
249
257
232
259
247
221
214


strength


Elongation
21.3
28.4
46.2
21.7
31.2
19.3
16.9
14.3


Liquid
X
X
Δ
Δ
◯
Δ
Δ
X


penetrant


testing


Leaching
X
X
◯
◯
◯
◯
◯
X


Machinability
—
86.4
83.1
81.6
72.7
73.1
74.9
80.2


coefficient


Surface
—
0.9
0.8
0.8
1.0
1.0
1.0
0.9


roughness


Shape of
—
◯
◯
◯
◯
◯
◯
◯


chips


Evaluation of
—
◯
◯
◯
◯
◯
◯
◯


Machinability


General
X
X
Δ
Δ
Δ
Δ
Δ
X








Example
Example
Example
Example
Example



Comparative
Comparative
14 of the
15 of the
7 of the
16 of the
17 of the
Comparative



Example 8
Example 9
invention
invention
invention
invention
invention
Example 10





Element


Ni
0.0
1.0
1.5
2.0
2.5
4.1
5.0
5.9


Sn
4.9
4.9
4.8
4.8
5.2
4.7
5.4
5.0


Zn
6.1
5.9
7.1
7.2
6.0
7.1
7.2
7.0


Bi
0.5
0.5
0.5
0.5
0.6
0.5
0.5
0.5


P
0.009
0.007
0.023
0.017
0.015
0.020
0.022
0.024


Si
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01


Pb
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001


Cu
Balance
Balance
Balance
Balance
Balance
Balance
Balance
Balance


Flowability of
Δ
Δ
Δ
◯
Δ
Δ
◯
Δ


molten metal


Mechanical
◯
◯
◯
◯
◯
◯
◯
X


properties


Tensile
270
274
233
259
273
278
288
269


strength


Elongation
45.3
36.5
20.8
27.1
26.8
22.5
20.8
13.5


Liquid
X
X
◯
◯
Δ
◯
◯
Δ


penetrant


testing


Leaching
X
◯
◯
◯
◯
◯
◯
◯


Machinability
—
85.2
83.1
75.7
76.7
71.8
75.3
66.6


coefficient


Surface
—
1.0
0.9
0.9
0.9
0.9
0.9
0.9


roughness


Shape of
—
◯
◯
◯
◯
◯
◯
X


chips


Evaluation of
—
◯
◯
◯
◯
◯
◯
X


Machinability


General
X
X
◯
◯
Δ
Δ
◯
X
























TABLE 3








Example 18
Example 2
Example 19
Example 7
Example 20




Comparative
of the
of the
of the
of the
of the
Comparative



Example 11
invention
invention
invention
invention
invention
Example 12























Element









Ni
2.5
2.5
2.5
2.5
2.5
2.5
2.5


Sn
1.0
2.0
2.7
3.9
5.2
5.9
8.4


Zn
7.1
7.2
6.0
7.1
6.0
7.2
8.2


Bi
0.6
0.5
0.6
0.5
0.6
0.5
0.6


P
0.021
0.023
0.017
0.020
0.015
0.019
0.019


Si
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01


Pb
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001


Cu
Balance
Balance
Balance
Balance
Balance
Balance
Balance


Flowability
Δ
Δ
Δ
Δ
Δ
Δ
◯


of molten


metal


Mechanical
◯
◯
◯
◯
◯
◯
X


properties


Tensile
230
252
259
264
273
267
253


strength


Elongation
44.2
31.0
31.2
32.9
26.8
20.7
12.4


Liquid
X
◯
◯
◯
Δ
◯
◯


penetrant


testing


Leaching
◯
◯
◯
◯
◯
◯
◯


Machinability
85.8
82.5
72.7
80.8
76.7
80.9
80.0


coefficient


Surface
1.0
0.9
0.8
1.0
0.9
0.8
0.8


roughness


Shape of
◯
◯
◯
◯
◯
◯
◯


chips


Evaluation of
◯
◯
◯
◯
◯
◯
◯


Machinability


General
X
Δ
Δ
Δ
Δ
Δ
X























TABLE 4









Example 2
Example 21
Example 22
Example 23
Example 24




Comparative
of the
of the
of the
of the
of the
Comparative



Example 13
invention
invention
invention
invention
invention
Example 14





Element


Ni
2.5
2.5
2.5
2.5
2.5
2.5
2.5


Sn
2.6
2.7
2.4
2.6
2.6
2.5
2.4


Zn
7.3
6.0
7.0
7.2
6.2
7.2
7.3


Bi
0.0
0.6
1.0
1.3
1.7
2.0
2.4


P
0.020
0.017
0.018
0.024
0.021
0.023
0.016


Si
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01


Pb
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001


Cu
Balance
Balance
Balance
Balance
Balance
Balance
Balance


Flowability of
Δ
Δ
Δ
◯
◯
Δ
X


molten metal


Mechanical
◯
◯
◯
◯
◯
◯
X


properties


Tensile
263
259
240
248
241
219
176


strength


Elongation
40.6
31.2
24.2
22.7
20.8
17.8
11.4


Liquid
X
◯
◯
◯
◯
◯
X


penetrant


testing


Leaching
X
◯
◯
◯
◯
◯
X


Machinability
61.1
72.7
85.9
—
84.2
91.3
86.1


coefficient


Surface
1.0
0.8
0.8
—
1.0
0.9
0.8


roughness


Shape of
X
◯
◯
—
◯
◯
◯


chips


Evaluation of
X
◯
◯
—
◯
◯
◯


Machinability


General
X
Δ
Δ
◯
◯
◯
X



















Example 7
Example 25
Example 26





Comparative
of the
of the
of the
Comparative




Example 15
invention
invention
invention
Example 16







Element



Ni
2.5
2.5
2.5
2.5
2.5



Sn
5.2
5.2
5.1
5.1
4.8



Zn
7.2
6.0
6.1
6.1
7.2



Bi
0.0
0.6
1.6
3.3
3.9



P
0.010
0.015
0.019
0.021
0.013



Si
<0.01
<0.01
<0.01
<0.01
<0.01



Pb
<0.001
<0.001
<0.001
<0.001
<0.001



Cu
Balance
Balance
Balance
Balance
Balance



Flowability of
X
Δ
◯
◯
◯



molten metal



Mechanical
◯
◯
◯
◯
X



properties



Tensile
298
273
270
237
189



strength



Elongation
47.4
26.8
24.1
16.6
8.8



Liquid
Δ
Δ
◯
◯
X



penetrant



testing



Leaching
◯
◯
◯
◯
◯



Machinability
61.8
76.7
86.7
90.2
96.9



coefficient



Surface
0.9
0.9
0.9
1.0
0.9



roughness



Shape of
X
◯
◯
◯
◯



chips



Evaluation of
X
◯
◯
◯
◯



Machinability



General
X
Δ
◯
◯
X























TABLE 5









Example 2
Example 27
Example 28
Example 29
Example 30



Comparative
of the
of the
of the
of the
of the



Example 17
invention
invention
invention
invention
invention





Element


Ni
2.5
2.5
2.7
2.5
2.5
2.5


Sn
2.6
2.7
2.7
2.6
2.6
2.5


Zn
7.2
6.0
7.8
7.1
7.2
7.3


Bi
0.5
0.6
0.6
0.5
0.5
0.4


P
0.002
0.017
0.039
0.049
0.100
0.150


Si
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01


Pb
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001


Cu
Balance
Balance
Balance
Balance
Balance
Balance


Flowability of
Δ
Δ
◯
Δ
Δ
◯


molten metal


Mechanical
◯
◯
◯
◯
◯
◯


properties


Tensile
228
259
269
263
281
265


strength


Elongation
25.4
31.2
34.6
35.2
29.1
17.6


Liquid
X
◯
◯
◯
◯
Δ


penetrant


testing


Leaching
◯
◯
◯
◯
◯
◯


Machinability
77.6
72.7
72.7
80.2
79.2
79.7


coefficient


Surface
0.9
0.8
0.7
0.9
0.9
0.7


roughness


Shape of chips
◯
◯
◯
◯
◯
◯


Evaluation of
◯
◯
◯
◯
◯
◯


Machinability


General
X
Δ
◯
Δ
Δ
Δ






Example 31
Example 32
Example 33
Example 34
Example 35
Example 36



of the
of the
of the
of the
of the
of the



invention
invention
invention
invention
invention
invention





Element


Ni
2.5
2.5
2.5
2.5
2.5
2.5


Sn
3.6
3.6
3.8
3.7
3.6
3.5


Zn
7.1
7.1
7.3
7.1
7.2
7.2


Bi
0.5
0.5
0.5
0.5
0.4
0.5


P
0.009
0.014
0.028
0.040
0.100
0.150


Si
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01


Pb
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001


Cu
Balance
Balance
Balance
Balance
Balance
Balance


Flowability of
Δ
Δ
Δ
Δ
Δ
◯


molten metal


Mechanical
◯
◯
◯
◯
◯
◯


properties


Tensile
261
254
263
270
267
293


strength


Elongation
35.6
32.4
29.7
29.5
20.2
26.0


Liquid
◯
◯
◯
Δ
Δ
Δ


penetrant


testing


Leaching
◯
◯
◯
◯
◯
◯


Machinability
75.7
80.0
79.9
79.1
75.2
76.4


coefficient


Surface
0.8
1.0
0.8
0.9
0.8
0.9


roughness


Shape of chips
◯
◯
◯
◯
◯
◯


Evaluation of
◯
◯
◯
◯
◯
◯


Machinability


General
Δ
Δ
Δ
Δ
Δ
Δ

















Example 7
Example 37
Example 38




Comparative
of the
of the
of the
Comparative



Example 18
invention
invention
invention
Example 19





Element


Ni
2.5
2.5
2.5
2.5
2.4


Sn
5.0
5.2
5.2
5.0
5.1


Zn
7.2
6.0
7.1
7.1
7.1


Bi
0.5
0.6
0.5
0.4
0.5


P
0.008
0.015
0.043
0.089
0.160


Si
<0.01
<0.01
<0.01
<0.01
<0.01


Pb
<0.001
<0.001
<0.001
<0.001
<0.001


Cu
Balance
Balance
Balance
Balance
Balance


Flowability of
◯
Δ
Δ
◯
Δ


molten metal


Mechanical
◯
◯
◯
◯
X


properties


Tensile
253
273
246
286
255


strength


Elongation
22.7
26.8
17.6
21.5
14.5


Liquid
X
Δ
◯
Δ
◯


penetrant


testing


Leaching
◯
◯
◯
◯
◯


Machinability
75.9
76.7
80.4
80.2
79.3


coefficient


Surface
0.9
0.9
0.9
0.9
0.8


roughness


Shape of chips
◯
◯
◯
◯
◯


Evaluation of
◯
◯
◯
◯
◯


Machinability


General
X
Δ
Δ
Δ
X























TABLE 6








Example 39







Comparative
of the
Comparative
Comparative
Comparative
Comparative



Example 1
invention
Example 20
Example 21
Example 22
Example 23






















Element








Ni
0.2
2.6
2.5
2.5
2.5
2.5


Sn
5.8
2.4
2.4
5.0
2.6
2.4


Zn
5.1
6.2
5.9
2.1
6.5
11.5


Bi
—
0.5
0.5
0.5
0.5
0.4


P
0.021
0.014
0.010
0.020
0.028
0.020


Si
—
<0.01
<0.01
0.02
0.25
0.25


Pb
5.4
0.2
0.5
<0.001
<0.001
<0.001


Cu
Balance
Balance
Balance
Balance
Balance
Balance


Flowability
Reference
Δ
Δ
X
◯
◯


of molten


metal


Mechanical

◯
◯
◯
◯
X


properties


Tensile
195
217
216
263
270
277


strength


Elongation
15
23.5
21.2
25.4
22.9
10.2


Liquid
Reference
Δ
X
Δ
X
X


penetrant


testing


Leaching
X
Δ
Δ
—
—
—


Machinability
Reference
75.9
—
—
—
—


coefficient


Surface

0.9
—
—
—
—


roughness


Shape of

◯
—
◯
◯


chips


Evaluation of

◯
—
—
—
—


Machinability


General

Δ
X
X
X
X









<Test for Flowability of Molten Metal>

The heated and melted copper alloy of each of examples of the invention and comparative examples was cast into the spiral test mold shown in FIG. 1 at a casting temperature of 1100 to 1200° C. The test mold is a spiral frame which comprises a plurality of quarter arc portions that are connected to each other. The initial quarter arc portion has a radius of 95 mm and includes graduations formed at equal intervals of 18.65 mm to divide the quarter arc portion into eight sections. The next quarter arc portion has a radius of 89 mm and has graduations arranged at equal intervals of 17.47 mm to divide the quarter arc into eight sections. Similarly, each of the other quarter arc portions are divided by graduations arranged at equal intervals into eight sections. Each of the figures in brackets in FIG. 1 indicates the intervals (mm) of the graduations in each quarter arc, and each of the numbers in circles indicates the number of the graduations present between the starting point and the circled number. In the test, the molten copper alloy of each example was cast into the space radially inside the portion of the frame indicated by the circled number 1. The point at which the molten alloy had ultimately reached is indicated in the table by the circled number of the quarter arc portion that is located radially outwardly of this point.
The numbers of the graduations (points) at which the reference material CAC406 (Comparative Example 1) had reached at the casting temperatures of 1100° C. and 1180° C. were 12.0 and 21.0, respectively. The numbers of the graduations for the other copper alloys are also shown in Table 7. The relations between the above points and the casting temperatures for the respective examples were plotted on the graph of FIG. 2, of which the vertical axis indicates the point at which each molten copper alloy had reached and the horizontal axis indicates the casting temperature. Of the plotted points on FIG. 2, those located above the line connecting the values for CAC406 and expressed by the below equation (3), i.e. those located above the right-angled triangle in FIG. 2, are indicated by symbols “◯”, those located below the above line for CAC406 but higher than 12.0 points at a casting temperature near 1200° C. are indicated by symbols “Δ”, and those located below 12.0 points even at a casting temperature near 1200° C. are indicated by “X” in view of practical operations. These results are shown in Table 7. In equation (3), X indicates the casting temperature and Y indicates the reference value of graduations.












TABLE 7







Casting
Ideal limit value





temperature
calculated from
Measurement
Flowability of



(° C.)
temperature
points
molten metal




















Example 1 of the
1161
≧18.9
13
Δ


invention


Example 2 of the
1182
≧21.2
18
Δ


invention


Example 3 of the
1160
≧18.8
18
Δ


invention


Example 4 of the
1167
≧19.5
21
◯


invention


Example 5 of the
1165
≧19.3
20
◯


invention


Example 6 of the
1165
≧19.3
15
Δ


invention


Example 7 of the
1172
≧20.1
17
Δ


invention


Example 8 of the
1150
≧17.6
18
◯


invention


Example 9 of the
1165
≧19.3
23
◯


invention


Example 10 of
1165
≧19.3
15
Δ


the invention


Example 11 of
1165
≧19.3
16
Δ


the invention


Example 12 of
1165
≧19.3
16
Δ


the invention


Example 13 of
1165
≧19.3
14
Δ


the invention


Example 14 of
1159
≧18.6
17
Δ


the invention


Example 15 of
1165
≧19.3
24
◯


the invention


Example 16 of
1157
≧18.4
14
Δ


the invention


Example 17 of
1157
≧18.4
22
◯


the invention


Example 18 of
1141
≧16.6
16
Δ


the invention


Example 19 of
1165
≧19.3
14
Δ


the invention


Example 20 of
1160
≧18.8
14
Δ


the invention


Example 21 of
1180
≧21.0
20
Δ


the invention


Example 22 of
1170
≧19.9
20
◯


the invention


Example 23 of
1156
≧18.3
19
◯


the invention


Example 24 of
1162
≧19.0
15
Δ


the invention


Example 25 of
1180
≧21.0
21
◯


the invention


Example 26 of
1180
≧21.0
25
◯


the invention


Example 27 of
1154
≧18.1
24
◯


the invention


Example 28 of
1165
≧19.3
19
Δ


the invention


Example 29 of
1165
≧19.3
13
Δ


the invention


Example 30 of
1161
≧18.9
23
◯


the invention


Example 31 of
1165
≧19.3
16
Δ


the invention


Example 32 of
1165
≧19.3
12
Δ


the invention


Example 33 of
1156
≧18.3
15
Δ


the invention


Example 34 of
1144
≧17.0
15
Δ


the invention


Example 35 of
1165
≧19.3
17
Δ


the invention


Example 36 of
1165
≧19.3
20
◯


the invention


Exaniple 37 of
1165
≧19.3
16
Δ


the invention


Example 38 of
1165
≧19.3
24
◯


the invention


Exampfe 39 of
1180
≧21.0
17
Δ


the invention


Comparative
1100
Reference
12
Reference


Example 1


Comparative
1180
Reference
21
Reference


Example 1


Comparative
1163
≧19.1
10
X


Example 2


Comparative
1160
≧18.8
11
X


Example 3


Comparative
1165
≧19.3
26
◯


Example 4


Comparative
1135
≧15.9
13
Δ


Example 5


Comparative
1150
≧17.6
15
Δ


Example 6


Comparative
1167
≧19.5
19
Δ


Example 7


Comparative
1147
≧17.3
15
Δ


Example 8


Comparative
1170
≧19.9
18
Δ


Example 9


Comparative
1165
≧19.3
17
Δ


Example 10


Comparative
1165
≧19.3
16
Δ


Example 11


Comparative
1180
≧21.0
23
◯


Example 12


Comparative
1160
≧18.8
13
Δ


Example 13


Comparative
1165
≧19.3
11
X


Example 14


Comparative
1165
≧19.3
11
X


Example 15


Comparative
1165
≧19.3
20
◯


Example 16


Comparative
1165
≧19.3
19
Δ


Example 17


Comparative
1165
≧19.3
20
◯


Example 18


Comparative
1165
≧19.3
19
Δ


Example 19


Comparative
1182
≧21.2
18
Δ


Example 20


Comparative
1200
≧23.3
8
X


Example 21


Comparative
1174
≧20.3
22
◯


Example 22


Comparative
1176
≧20.6
27
◯


Example 23









Y=0.1125×X−111.75  (3)

<Test for Mechanical Properties>

For the respective alloys, type A test specimens under JIS H 5120 were cast and then type 4 test specimens were machined under JIS Z 2201. Under JIS Z 2241, their tensile strength and elongation were measured. The results are shown in Table 8, and their evaluations are shown in Tables 1 to 6. Compared to Comparative Example 1 as the reference material, if both the tensile strength (MPa) and the elongation (%) are superior, the symbol “◯” is given, and if either of them is inferior, the symbol “X” is given.











TABLE 8 







Tensile





strength
Elongation
Mechanical



(MPa)
(%)
properties



















Example 1 of the invention
246
27.8
◯


Example 2 of the invention
259
31.2
◯


Example 3 of the invention
253
33.9
◯


Example 4 of the invention
248
34.7
◯


Example 5 of the invention
232
31.1
◯


Example 6 of the invention
293
31.4
◯


Example 7 of the invention
273
26.8
◯


Example 8 of the invention
273
28.0
◯


Example 9 of the invention
251
24.1
◯


Example 10 of the invention
257
46.2
◯


Example 11 of the invention
232
21.7
◯


Example 12 of the invention
247
19.3
◯


Example 13 of the invention
221
16.9
◯


Example 14 of the invention
233
20.8
◯


Example 15 of the invention
259
27.1
◯


Example 16 of the invention
278
22.5
◯


Example 17 of the invention
288
20.8
◯


Example 18 of the invention
252
31.0
◯


Example 19 of the invention
264
32.9
◯


Example 20 of the invention
267
20.7
◯


Example 21 of the invention
240
24.2
◯


Example 22 of the invention
248
22.7
◯


Example 23 of the invention
241
20.8
◯


Example 24 of the invention
219
17.8
◯


Example 25 of the invention
270
24.1
◯


Example 26 of the invention
237
16.6
◯


Example 27 of the invention
269
34.6
◯


Example 28 of the invention
263
35.2
◯


Example 29 of the invention
281
29.1
◯


Example 30 of the invention
265
17.6
◯


Example 31 of the invention
261
35.6
◯


Example 32 of the invention
254
32.4
◯


Example 33 of the invention
263
29.7
◯


Example 34 of the invention
270
29.5
◯


Example 35 of the invention
267
20.2
◯


Example 36 of the invention
293
26.0
◯


Example 37 of the invention
246
17.6
◯


Example 38 of the invention
286
21.5
◯


Example 39 of the invention
217
23.5
◯


Comparative Example 1
≧195
≧15
Reference


Comparative Example 2
274
34.8
◯


Comparative Example 3
289
32.9
◯


Comparative Example 4
207
14.1
X


Comparative Example 5
215
21.3
◯


Comparative Example 6
249
28.4
◯


Comparative Example 7
214
14.3
X


Comparative Example 8
270
45.3
◯


Comparative Example 9
274
36.5
◯


Comparative Example 10
269
13.5
X


Comparative Example 11
230
44.2
◯


Comparative Example 12
253
12.4
X


Comparative Example 13
263
40.6
◯


Comparative Example 14
176
11.4
X


Comparative Example 15
298
47.4
◯


Comparative Example 16
189
8.8
X


Comparative Example 17
228
25.4
◯


Comparative Example 18
253
22.7
◯


Comparative Example 19
255
14.5
X


Comparative Example 20
216
21.2
◯


Comparative Example 21
263
25.4
◯


Comparative Example 22
270
22.9
◯


Comparative Example 23
277
10.2
X









<Liquid Penetrant Testing for Stepped Test Specimens>

As shown in FIG. 3, a stepped CO2 mold was prepared having three stepped portions having wall thicknesses of 20, 30 and 40 mm, respectively, to reduce the feeding effect, thereby making the test specimens more prone to casting defects. The castings produced by this mold were cut at their central portions and were subjected to a liquid penetrant testing under JIS Z 2343. In the test, the specimens were observed to determine whether they suffered casting defects and/or microporosity. The symbol “◯” is given to specimens on which no pattern that indicates defects was found at their central portions in their wall thickness direction, and which can thus be produced by the same casting method as used for the reference material JIS CAC406. The symbol “Δ” (passable) is given to specimens on which a pattern that indicates defects was found at their central portions in their wall thickness direction, but which can still be produced by the same casting method as used for the reference material. But the castings to which the symbol “Δ” is given could suffer defects according to their shapes and the casting conditions. Thus, in producing them, their casting method and the like should also be taken into consideration. The symbol “X” is given to other castings. The test results are shown in the respective tables. Among them, photos of selected examples of the invention and comparative examples are shown in FIGS. 4(a) to 4(e). Among them, stain-like patterns seen on the outer perimeters of the sections of Examples 3, 20, 23, 25-28, 31-34, 36 and 39, of the invention, and Comparative Example 12 were caused by the coloring of the penetrant and have nothing to do with casting defects.
<Leaching Test>
The test was conducted based on a leaching test method under JWWA Z 108 and an analysis method of leachate under JWWA Z 110, both set by Japan Water Works Association. The test results are shown in Table 9, and their general evaluations are shown in Tables 1 to 6. The test was conducted with the ratio of contact area between the test pieces and the leaching solution set at 1000 cm2/l, except Example 27 of the invention, of which the test was conducted under more harsh leaching conditions of 2000 cm2/l. For the leaching amounts of lead, zinc and copper, determination was made using values of which their upper limits had been corrected to 100-fold values. For lead, however, for leaching values that exceeded the reference value of 0.001 mg/l, values corrected by multiplying these values by 1/100 are also described in the table as values used for actual determination. For zinc and copper too, for values that exceeded their reference values, values corrected by multiplying these values by 1/100 are also described in the table. These corrected values are ordinarily used as decision criteria because it is extremely difficult to achieve the predetermined reference values. The symbol “◯” is given to specimens which satisfy the requirements without correction (not more than 0.001 mg/l) for lead, and which at least satisfy the requirements after correction for elements other than lead. The symbol “Δ” is given to specimens which does not satisfy the requirements without correction for lead, and which satisfy the requirements after correction for other elements. The symbol “X” is given to specimens which neither satisfy the requirements without correction for lead, and the requirements after correction for other elements. Comparative Example 1, which contains 4 to 6% by weight of lead, does not satisfy the leaching requirements for lead even after correction. The symbol “X” is given to Comparative Examples 5 to 8, 13 and 14, because these examples do not satisfy the requirements for chromaticity.










TABLE 9









Leaching value (mg/l)


















Pb
Zn
Cu
Cd


Chromaticity
Turbidity
Leaching



(≦0.001)
(≦0.1)
(≦0.1)
(≦0.001)
Taste
Odor
(≦0.5)
(≦0.2)
properties




















Example 1 of
<0.0005
0.55 (after
0.10
<0.0001
No
No
0.2
<0.01
◯


the invention

correction


abnormality
abnormality




0.0055)


Example 2 of
<0.0005
0.52 (after
0.09
<0.0001
No
No
0.3
<0.01
◯


the invention

correction


abnormality
abnormality




0.0052)


Example 3 of
<0.0005
0.92 (after
0.06
<0.0001
No
No
0.5
<0.01
◯


the invention

correction


abnormality
abnormality




0.0092)


Example 4 of
<0.0005
1.00 (after
0.07
<0.0001
No
No
0.2
<0.01
◯


the invention

correction


abnormality
abnormality




0.0100)


Example 5 of
<0.0005
1.08 (after
0.06
<0.0001
No
No
0.4
<0.01
◯


the invention

correction


abnormality
abnormality




0.0108)


Example 6 of
<0.0005
0.42 (after
0.06
<0.0001
No
No
0.3
<0.01
◯


the invention

correction


abnormality
abnormality




0.0042)


Example 7 of
<0.0005
0.40 (after
0.07
<0.0001
No
No
0.4
<0.01
◯


the invention

correction


abnormality
abnormality




0.0040)


Example 8 of
<0.0005
0.68 (after
0.05
<0.0001
No
No
0.5
<0.01
◯


the invention

correction


abnormality
abnormality




0.0068)


Example 9 of
<0.0005
0.89 (after
0.07
<0.0001
No
No
0.2
<0.01
◯


the invention

correction


abnormality
abnormality




0.0089)


Example 10 of
<0.0005
0.87 (after
0.11 (after
<0.0001
No
No
0.5
0.02
◯


the invention

correction
correction

abnormality
abnormality




0.0087)
0.0011)


Example 11 of
<0.0005
0.78 (after
0.09
<0.0001
No
No
0.5
<0.01
◯


the invention

correction


abnormality
abnormality




0.0078)


Example 12 of
<0.0005
0.40 (after
0.06
<0.0001
No
No
0.4
<0.01
◯


the invention

correction


abnormality
abnormality




0.0040)


Example 13 of
<0.0005
0.33 (after
0.05
<0.0001
No
No
0.2
<0.01
◯


the invention

correction


abnormality
abnormality




0.0033)


Example 14 of
<0.0005
0.77 (after
0.10
<0.0001
No
No
0.4
<0.01
◯


the invention

correction


abnormality
abnormality




0.0077)


Example 15 of
<0.0005
0.68 (after
0.09
<0.0001
No
No
0.3
<0.01
◯


the invention

correction


abnormality
abnormality




0.0068)


Example 16 of
<0.0005
0.53 (after
0.04
<0.0001
No
No
0.4
<0.01
◯


the invention

correction


abnormality
abnormality




0.0053)


Example 17 of
<0.0005
0.48 (after
0.04
<0.0001
No
No
0.3
<0.01
◯


the invention

correction


abnormality
abnormality




0.0048)


Example 18 of
<0.0005
0.58 (after
0.11 (after
<0.0001
No
No
0.5
<0.01
◯


the invention

correction
correction

abnormality
abnormality




0.0058)
0.0011)


Example 19 of
<0.0005
0.49 (after
0.09
<0.0001
No
No
0.4
<0.01
◯


the invention

correction


abnormality
abnormality




0.0049)


Example 20 of
<0.0005
0.42 (after
0.05
<0.0001
No
No
0.2
<0.01
◯


the invention

correction


abnormality
abnormality




0.0042)


Example 21 of
<0.0005
0.66 (after
0.09
<0.0001
No
No
0.5
<0.01
◯


the invention

correction


abnormality
abnormality




0.0066)


Example 22 of
<0.0005
0.70 (after
0.07
<0.0001
No
No
0.5
<0.01
◯


the invention

correction


abnormality
abnormality




0.0070)


Example 23 of
<0.0005
0.50 (after
0.08
<0.0001
No
No
0.5
<0.01
◯


the invention

correction


abnormality
abnormality




0.0050)


Example 24 of
<0.0005
0.48 (after
0.09
<0.0001
No
No
0.4
<0.01
◯


the invention

correction


abnormality
abnormality




0.0048)


Example 25 of
<0.0005
0.43 (after
0.07
<0.0001
No
No
0.5
<0.01
◯


the invention

correction


abnormality
abnormality




0.0043)


Example 26 of
<0.0005
0.51 (after
0.06
<0.0001
No
No
0.4
<0.01
◯


the invention

correction


abnormality
abnormality




0.0051)


Example 27 of
<0.0005
1.50 (after
0.06
<0.0001
No
No
0.5
<0.01
◯


the invention

correction


abnormality
abnormality




0.0150)


Example 28 of
<0.0005
0.48 (after
0.07
<0.0001
No
No
0.4
<0.01
◯


the invention

correction


abnormality
abnormality




0.0048)


Example 29 of
<0.0005
0.51 (after
0.05
<0.0001
No
No
0.4
<0.01
◯


the invention

correction


abnormality
abnormality




0.0051)


Example 30 of
<0.0005
0.57 (after
0.05
<0.0001
No
No
0.3
<0.01
◯


the invention

correction


abnormality
abnormality




0.0057)


Example 31 of
<0.0005
1.05 (after
0.09
<0.0001
No
No
0.5
<0.01
◯


the invention

correction


abnormality
abnormality




0.0105)


Example 32 of
<0.0005
0.71 (after
0.10
<0.0001
No
No
0.3
<0.01
◯


the invention

correction


abnormality
abnormality




0.0071)


Example 33 of
<0.0005
0.58 (after
0.09
<0.0001
No
No
0.4
<0.01
◯


the invention

correction


abnormality
abnormality




0.0058)


Example 34 of
<0.0005
0.54 (after
0.06
<0.0001
No
No
0.3
<0.01
◯


the invention

correction


abnormality
abnormality




0.0054)


Example 35 of
<0.0005
0.56 (after
0.07
<0.0001
No
No
0.3
<0.01
◯


the invention

correction


abnormality
abnormality




0.0056)


Example 36 of
<0.0005
0.52 (after
0.07
<0.0001
No
No
0.4
<0.01
◯


the invention

correction


abnormality
abnormality




0.0052)


Example 37 of
<0.0005
0.59 (after
0.05
<0.0001
No
No
0.4
<0.01
◯


the invention

correction


abnormality
abnormality




0.0059)


Example 38 of
<0.0005
0.45 (after
0.05
<0.0001
No
No
0.4
<0.01
◯


the invention

correction


abnormality
abnormality




0.0045)


Example 39 of
0.029 (after
0.62 (after
0.08
<0.0001
No
No
0.5
0.06
Δ


the invention
correction
correction


abnormality
abnormality



0.00029)
0.0062)


Comparative
0.38 (after
0.31 (after
0.08
0.0004
No
No
0.5
0.08
Reference


Example 1
correction
correction


abnormality
abnormality


material X



0.0038)
0.0031)


Comparative
<0.0005
0.23 (after
0.15 (after
<0.0001
No
No
0.5
<0.01
◯


Example 2

correction
correction

abnormality
abnormality




0.0023)
0.0015)


Comparative
<0.0005
0.32 (after
0.10 (after
<0.0001
No
No
0.5
<0.01
◯


Example 3

correction
correction

abnormality
abnormality




0.0032)
0.0010)


Comparative
<0.0005
1.22 (after
0.05
<0.0001
No
No
0.5
<0.01
◯


Example 4

correction


abnormality
abnormality




0.0122)


Comparative
<0.0005
1.12 (after
0.18 (after
<0.0001
No
No
0.6
0.05
X


Example 5

correction
correction

abnormality
abnormality




0.0112)
0.0018)


Comparative
<0.0005
1.00 (after
0.13 (after
<0.0001
No
No
0.6
0.02
X


Example 6

correction
correction

abnormality
abnormality




0.0100)
0.0013)


Comparative
<0.0005
0.40 (after
0.11 (after
<0.0001
No
No
0.7
0.07
X


Example 7

correction
correction

abnormality
abnormality




0.0040)
0.0011)


Comparative
<0.0005
1.20 (after
0.12 (after
<0.0001
No
No
0.7
0.06
X


Example 8

correction
correction

abnormality
abnormality




0.0120)
0.0012)


Comparative
<0.0005
0.98 (after
0.09
<0.0001
No
No
0.5
<0.01
◯


Example 9

correction


abnormality
abnormality




0.0098)


Comparative
<0.0005
0.38 (after
0.03
<0.0001
No
No
0.4
<0.01
◯


Example 10

correction


abnormality
abnormality




0.0038)


Comparative
<0.0005
0.82 (after
0.12 (after
<0.0001
No
No
0.4
<0.01
◯


Example 11

correction
correction

abnormality
abnormality




0.0082)
0.0012)


Comparative
<0.0005
0.72 (after
0.04
<0.0001
No
No
0.4
<0.01
◯


Example 12

correction


abnormality
abnormality




0.0072)


Comparative
<0.0005
1.18 (after
0.16 (after
<0.0001
No
No
0.7
0.07
X


Example 13

correction
correction

abnormality
abnormality




0.0118)
0.0016)


Comparative
<0.0005
0.82 (after
0.12 (after
<0.0001
No
No
0.6
<0.01
X


Example 14

correction
correction

abnormality
abnormality




0.0082)
0.0012)


Comparative
<0.0005
0.98 (after
0.11 (after
<0.0001
No
No
0.5
<0.01
◯


Example 15

correction
correction

abnormality
abnormality




0.0098)
0.0011)


Comparative
<0.0005
0.85 (after
0.14 (after
<0.0001
No
No
0.5
<0.01
◯


Example 16

correction
correction

abnormality
abnormality




0.0085)
0.0014)


Comparative
<0.0005
1.12 (after
0.13 (after
<0.0001
No
No
0.5
0.05
◯


Example 17

correction
correction

abnormality
abnormality




0.0112)
0.0013)


Comparative
<0.0005
1.01 (after
0.13 (after
<0.0001
No
No
0.4
0.03
◯


Example 18

correction
correction

abnormality
abnormality




0.0101)
0.0013)


Comparative
<0.0005
0.48 (after
0.12 (after
<0.0001
No
No
0.2
<0.01
◯


Example 19

correction
correction

abnormality
abnormality




0.0048)
0.0012)


Comparative
0.061 (after
0.55 (after
0.09
<0.0001
No
No
0.5
0.05
Δ


Example 20
correction
correction


abnormality
abnormality



0.00061)
0.0055)









<Test for Machinability>

Using a cemented carbide tool, the respective copper alloy specimens were lathed at a cutting speed of 400 (m/min), with a depth of cut of 1.0 mm and a feed rate of 0.1 mm/rev., and the influence of cutting on each specimen was determined according to the machinability coefficient, surface roughness and the shapes of powder chips. These results are shown in the respective tables. As an alloy that shows ideal machinability, the alloy of Comparative Example 1 (CAC406) was also evaluated for surface roughness and the shapes of powder chips. The results are shown in Table 10 as well as in Tables 1 to 6. For Example 27 of the invention and Comparative Example 1, measurements were made for two different cutting speeds of 100 (m/min) and 200 (m/min). But no significant differences were observed according to a difference in cutting speed.













TABLE 10 







Machining
Machinability
Surface





speed
coefficient
roughness

Evaluation of



(m/min)
≧70
(μm)
Shape of chips
Machinability





















Example 1 of the
400
77.9
0.8
◯
◯


invention


Example 2 of the
400
72.7
0.8
◯
◯


invention


Example 4 of the
400
80.8
0.9
◯
◯


invention


Example 5 of the
400
81.3
1.0
◯
◯


invention


Example 6 of the
400
75.2
0.9
◯
◯


invention


Example 7 of the
400
76.7
0.9
◯
◯


invention


Example 9 of the
400
79.1
1.1
◯
◯


invention


Example 10 of
400
83.1
0.8
◯
◯


the invention


Example 11 of
400
81.6
0.8
◯
◯


the invention


Example 12 of
400
73.1
1.0
◯
◯


the invention


Example 13 of
400
74.9
1.0
◯
◯


the invention


Example 14 of
400
83.1
0.9
◯
◯


the invention


Example 15 of
400
75.7
0.9
◯
◯


the invention


Example 16 of
400
71.8
0.9
◯
◯


the invention


Example 17 of
400
75.3
0.9
◯
◯


the invention


Example 18 of
400
82.5
0.9
◯
◯


the invention


Example 19 of
400
80.8
1.0
◯
◯


the invention


Example 20 of
400
80.9
0.8
◯
◯


the invention


Example 21 of
400
85.9
0.8
◯
◯


the invention


Example 23 of
400
84.2
1.0
◯
◯


the invention


Example 24 of
400
91.3
0.9
◯
◯


the invention


Example 25 of
400
86.7
0.9
◯
◯


the invention


Example 26 of
400
90.2
1.0
◯
◯


the invention


Example 27 of
400
72.7
0.7
◯
◯


the invention


Example 27 of
200
73.2
0.6
◯
◯


the invention


Example 27 of
100
74.5
0.8
◯
◯


the invention


Example 28 of
400
80.2
0.9
◯
◯


the invention


Example 29 of
400
79.2
0.9
◯
◯


the invention


Example 30 of
400
79.7
0.7
◯
◯


the invention


Example 31 of
400
75.7
0.8
◯
◯


the invention


Example 32 of
400
80.0
1.0
◯
◯


the invention


Example 33 of
400
79.9
0.8
◯
◯


the invention


Example 34 of
400
79.1
0.9
◯
◯


the invention


Example 35 of
400
75.2
0.8
◯
◯


the invention


Example 36 of
400
76.4
0.9
◯
◯


the invention


Example 37 of
400
80.4
0.9
◯
◯


the invention


Example 38 of
400
80.2
0.9
◯
◯


the invention


Example 39 of
400
75.9
0.9
◯
◯


the invention


Comparative
400
100.0
0.8
Reference
Reference


Example 1


Comparative
200
100.0
0.8
Reference
Reference


Example 1


Comparative
100
100.0
1.0
Reference
Reference


Example 1


Comparative
400
71.2
0.8
◯
◯


Example 2


Comparative
400
73.5
0.9
◯
◯


Example 3


Comparative
400
78.5
0.9
◯
◯


Example 4


Comparative
400
86.4
0.9
◯
◯


Example 6


Comparative
400
80.2
0.9
◯
◯


Example 7


Comparative
400
85.2
1.0
◯
◯


Example 9


Comparative
400
66.6
0.9
◯
X


Example 10


Comparative
400
85.8
1.0
◯
◯


Example 11


Comparative
400
80.0
0.8
◯
◯


Example 12


Comparative
400
61.1
1.0
X
X


Example 13


Comparative
400
86.1
0.8
◯
◯


Example 14


Comparative
400
61.8
0.9
X
X


Example 15


Comparative
400
96.9
0.9
◯
◯


Example 16


Comparative
400
77.6
0.9
◯
◯


Example 17


Comparative
400
75.9
0.9
◯
◯


Example 18


Comparative
400
79.3
0.8
◯
◯


Example 19









The machinability coefficients were calculated from three stresses (resultant of three stresses) of the respective examples and three stresses (resultant of three forces) of CAC406 as a comparative material as measured by AST-TTH made by Sato Kogyo Co., Ltd. as a type AST cutting tool dynamometer, using the abovementioned equations (1) and (2). Specimens of which the machinability coefficient is 70 or higher were determined to be good. For Comparative Examples 10, 13 and 15, the machinability coefficients were less than 70. The cutting resistance was so large that it was necessary to reduce the cutting speed. Productivity is thus low.
The surface roughness was measured using a surface roughness meter (made by Mitsutoyo Corporation: Surftest-4), and the respective surface roughness values were compared with the surface roughness of the comparative material CAC406 (Comparative Example 1). At any cutting speed, the surface roughness values of the copper alloy specimens of examples of the invention were larger only by 0.3 μm at the most than the surface roughness value of the comparative material, so that their finish was equivalent to that of the comparative material. These results are shown in the respective tables.
The powder chips were evaluated according to their shapes by classifying their shaped as shown in FIG. 5. The shapes of powder chips produced from the respective examples are shown in FIGS. 6(a) to 6(e). The symbols “◯” and “X” are given to examples of which the shapes of chips are good and no good, respectively. Examples 7 and 21 of the invention, of which the bismuth contents are 0.6% by weight and 1.0% by weight, respectively, both produced broken chips. Examples 25 and 23 of the invention, of which the bismuth contents are 1.6% by weight and 1.7% by weight, respectively, produced broken chips at high cutting speeds. Example 26 of the invention, of which the bismuth content is 3.3% by weight, produced ideal sheared chips. The higher the bismuth content, the more ideal the shapes of chips become. But Example 23 of the invention, of which the bismuth content is higher by 0.1% by weight than Example 25, produced broken chips. On the other hand, Example 25 produced ideal sheared chips in spite of the fact that its bismuth content is lower by 0.1% by weight than Example 23. This indicates that Example 25, of which the tin content is twice that of Example 23, produces larger amounts of nickel-tin compounds, which serve as chip breakers in the same manner as bismuth. On the other hand, Comparative Examples 13 and 15 produced long helical chips. Such chips tend to increasing the temperature of the cutting tool, thereby shortening the lifespan of the tool. The added values in Example 27 of the invention and Comparative Example 1 indicate cutting speed (m/min). For all the other examples, the cutting speed was 40 (m/min).
(Consideration about the Zinc Content)
As shown in Table 1, copper alloy specimens were prepared of which the zinc contents are significantly different from each other with the contents of other elements as close to each other as possible. The above measurements were made for these specimens. Comparative Example 2 and Examples 1 to 5 of the invention contained about 2.5% by weight of tin, while Comparative Examples 3 and 4 and Examples 6 to 9 of the invention contained about 5.0% by weight of tin. In either case, for Comparative Examples 2 and 3, of which the zinc contents are less than 5% by weight, evaluations of flowability of molten metal and liquid penetrant testing were both “X”. In the table, the contents of the respective elements are in weight percent, the tensile strength is in (MPa), and the elongation is in (%).
(Consideration about the Nickel Content)
As shown in Table 2, copper alloy specimens Were prepared of which the nickel contents are significantly different from each other with the contents of other elements as close to each other as possible. The above measurements were made for these specimens. Comparative Examples 5 to 7 and Examples 2 and 10 to 13 of the invention contained about 2.5% by weight of tin, while Comparative Examples 8 to 10 and Examples 7 and 14 to 17 of the invention contained about 5.0% by weight of tin. Comparative Examples 5, 6, 8 and 9, of which the nickel contents are less than 1.5% by weight, developed microporosity and the like, irrespective of the tin contents. Comparative Examples 5 and 8, of which the nickel contents are low, caused problems in the leaching test too. On the other hand, Comparative Examples 7 and 10, of which the nickel contents are higher than 5.0% by weight, the elongation was too low. Comparative Example 10, which contained a large amount of tin, was inferior in machinability.
(Consideration about the Tin Content)
As shown in Table 3, copper alloy specimens were prepared of which the tin contents are significantly different from each other with the contents of other elements as close to each other as possible. The above measurements were made for these specimens. Comparative Example 11, of which the tin content was less than 2.0% by weight, developed microporosity and the like. On the other hand, Comparative Example 12, of which the tin content is higher than 5.9% by weight, was too low in the elongation.
(Consideration about the Bismuth Content)
As shown in Table 4, copper alloy specimens were prepared of which the bismuth contents are significantly different from each other with the contents of other elements as close to each other as possible. The above measurements were made for these specimens. Comparative Examples 13 and 14 and Examples 2 and 21 to 24 of the invention contained about 2.5% by weight of tin, while Comparative Examples 15 and 16 and Examples 7, 25 and 26 of the invention contained about 5.0% by weight of tin. Comparative Examples 13 and 15, of which the bismuth contents are less than 0.4% by weight, caused problems in machinability. Comparative Example 13 developed microporosity. Comparative Example 15 caused problems in flowability of molten metal. On the other hand, while Example 26, which contained about 5% by weight of tin, showed favorable properties even though the bismuth content is 3.3% by weight, Comparative Example 14, which contained 2.4% by weight of tin, caused problems in flowability of molten metal and mechanical properties when the bismuth content was 2.4% by weight. This indicates that the permissible bismuth content varies with the tin content.
(Consideration about the Phosphorus Content)
As shown in Table 5, copper alloy specimens were prepared of which the phosphorus contents are significantly different from each other with the contents of other elements as close to each other as possible. The above measurements were made for these specimens. Comparative Example 17 and Examples 2 and 27 to 30 of the invention contained about 2.5% by weight of tin, while Examples 31 to 36 of the invention contained about 3.5% by weight of tin, and Comparative Examples 18 and 19 and Examples 7, 37 and 38 of the invention contained about 5.0% by weight of tin. Comparative Examples 17 and 18, of which the phosphorus contents are less than 0.009% by weight, developed microporosity. On the other hand, Comparative Example 19, of which the phosphorus content is higher than 0.15% by weight, was too low in the elongation, so that it had a problem in mechanical properties. For comparison, the values in Table 5 are those when the cutting speed was 400 m/min.
(Consideration of Large Amounts of Impurities)
As shown in Table 6, copper alloys containing 0.2% by weight of lead (Example 39 of the invention) and containing 0.5% by weight of lead (Comparative Example 20) were prepared, and the above measurements were made. Example 38 satisfied every standard. But in Comparative Example 20, microporosity and the like deteriorated to an unignorable level.
As shown in Table 6, copper alloys containing silicon by amounts higher than the detection limit, i.e. 0.02% by weight and 0.25% by weight (Comparative Examples 21 to 23) were prepared, and the above measurements were made. Comparative Example 21, of which the silicon content is 0.02% by weight, was inferior in flowability of molten metal, while Comparative Examples 22 and 23, of which the silicon contents are 0.25% by weight, developed microporosity and the like.
(Metallographic Analysis Using EPMA)
For the alloys of selected examples, metallographic analysis in the form of mapping analysis of the respective elements was carried out using EPMA-8705 made by Shimadzu Corporation to confirm the distributions of the respective elements and the formation of compounds. The elements examined were copper, nickel, tin, zinc, phosphorus and bismuth. Their distributions and the form of compounds were examined.
Among these examples, examination was selectively made for the examples used for consideration about nickel, tin, bismuth and phosphorus. FIGS. 7(a) to 7(i) show the results of 360-times mapping analysis thereof. Comparison of these element contents reveals that by adding nickel, nickel-tin compounds and nickel-phosphorus compounds form. The surface rate of nickel compound and bismuth, which are considered to be involved in the amount of microporosity, was measured using GRADING ANALYSIS made by Keyence Corporation.
Specifically, the results of analysis by EPMA-8705 were formed into images using data processing software H5 that is attached to this device. Using this software, nickel and phosphorus, nickel and tin, and bismuth element were individually synthesized and images were formed for the overlapping portions by digital data. Based on these data, analysis was made by the abovementioned GRADING ANALYSIS. The results of analysis and measurement are shown in Table 11.














TABLE 11







Contents of








elements
Bi
Ni—P
Ni—Sn
Total area rate of
Total area rate of



considered
area rate
area rate
area rate
Ni compounds
Bi + Ni compounds



(weight %)
(%)
(%)
(%)
(%)
(%)






















Nickel range








Example 10 of
1.5
0.68
0.02
0.02
0.04
0.72


the invention


Example 2 of
2.5
0.71
0.07
0.06
0.13
0.85


the invention


Example 13 of
5.0
1.36
0.31
0.78
1.10
2.46


the invention


Example 14 of
1.5
0.76
0.03
0.24
0.27
1.03


the invention


Example 17 of
5.0
0.37
0.32
0.59
0.92
1.28


the invention


Tin range


Example 18 of
2.0
0.62
0.11
0.03
0.13
0.76


the invention


Example 2 of
2.7
0.71
0.07
0.06
0.13
0.85


the invention


Example 19 of
3.9
0.65
0.08
0.09
0.17
0.82


the invention


Example 7 of
5.2
0.94
0.08
0.35
0.44
1.38


the invention


Example 20 of
5.9
1.22
0.21
1.74
1.95
3.17


the invention


Bismuth


range


Example 2 of
0.6
0.71
0.07
0.06
0.13
0.85


the invention


Example 23 of
1.7
2.15
0.06
0.17
0.23
2.37


the invention


Example 24 of
2.0
2.19
0.02
0.11
0.14
2.33


the invention


Example 7 of
0.6
0.94
0.08
0.35
0.44
1.38


the invention


Example 26 of
3.3
4.55
0.11
1.29
1.40
5.95


the invention


Phosphorus


range


Example 2 of
0.017
0.71
0.07
0.06
0.13
0.85


the invention


Example 27 of
0.039
0.53
0.19
0.19
0.39
0.91


the invention


Example 30 of
0.150
0.38
0.42
0.00
0.42
0.80


the invention









In the consideration according to the nickel, tin and phosphorus contents, the area ratios of nickel-tin compounds and nickel-phosphorus compounds increased with increases in the contents of the elements considered. In order to consider these compounds in more detail, for Examples 13, 23 and 26 of the invention, further enlarged 2000-fold mapping analysis was carried out. As a result, it was discovered that nickel, tin and phosphorus compounds deposited near bismuth. This shows that they serve to fill microporosity.

## Claims

1. A copper alloy member for use in water works consisting essentially of not less than 2.0% by weight and not more than 5.9% by weight of tin, not less than 1.5% by weight and not more than 5.0% by weight of nickel, not less than 5.0% by weight and not more than 12.1% by weight of zinc, not less than 0.4% by weight and not more than 3.3% by weight of bismuth, and not less than 0.009% by weight and not more than 0.15% by weight of phosphorus, the balance being copper and impurities.

2. The copper alloy member for use in water works according to claim 1, wherein said impurities include lead of which the content is not more than 0.2% by weight, and silicon of which the content is less than 0.01% by weight.

3. The copper alloy member for use in water works according to claim 1, wherein the content of said bismuth is not less than 0.4% by weight and not more than 2.0% by weight.

4. The copper alloy member for use in water works according to claim 1, wherein the content of said tin is not less than 5.1% by weight and not more than 5.2% by weight.

5. The copper alloy member for use in water works according to claim 2, wherein the content of said bismuth is not less than 0.4% by weight and not more than 2.0% by weight.

6. The copper alloy member for use in water works according to claim 2, wherein the content of said tin is not less than 5.1% by weight and not more than 5.2% by weight.