U.S. patent application number 10/478454 was filed with the patent office on 2004-11-25 for high-strength copper alloy.
Invention is credited to Oishi, Keiichiro, Otani, Junichi, Sasaki, Isao.
Application Number | 20040234412 10/478454 |
Document ID | / |
Family ID | 31973177 |
Filed Date | 2004-11-25 |
United States Patent
Application |
20040234412 |
Kind Code |
A1 |
Oishi, Keiichiro ; et
al. |
November 25, 2004 |
High-strength copper alloy
Abstract
The present invention is a high strength copper alloy that is
superior to mechanical properties, workability, corrosion
resistance and economy. The present invention discloses high
strength copper alloy characterized in that said copper alloy
consists essentially of 4 to 19 mass percent of Zn, 0.5 to 2.5 mass
percent of Si and the remaining mass percent of Cu, wherein said
mass percent of Zn and said mass percent of Si satisfy the
relationship Zn-2.5.Si=0 to 15 mass percent; mean grain size D of
crystalline structure of said copper alloy distributes in 0.3
.mu.m.ltoreq.D.ltoreq.3.5 .mu.m; and 0.2% yield strength in
recrystallization state of said copper alloy is higher than 250
N/mm.sup.2.
Inventors: |
Oishi, Keiichiro;
(Sakai-shi, JP) ; Sasaki, Isao; (Sakai-shi,
JP) ; Otani, Junichi; (Sakai-shi, JP) |
Correspondence
Address: |
Koda & Androlia
Suite 1430
2029 Century Park East
Los Angeles
CA
90067-3024
US
|
Family ID: |
31973177 |
Appl. No.: |
10/478454 |
Filed: |
November 21, 2003 |
PCT Filed: |
April 8, 2003 |
PCT NO: |
PCT/JP03/04470 |
Current U.S.
Class: |
420/477 |
Current CPC
Class: |
C22F 1/08 20130101; C22C
9/04 20130101; H01H 1/025 20130101 |
Class at
Publication: |
420/477 |
International
Class: |
C22C 009/04 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 9, 2002 |
JP |
2002-263125 |
Claims
1. A high strength copper alloy characterized in that said copper
alloy consists essentially of 4 to 19 mass percent of Zn, 0.5 to
2.5 mass percent of Si and the remaining mass percent of Cu,
wherein said mass percent of Zn and said mass percent of Si satisfy
the relationship Zn-2.5.Si=0 to 15 mass percent; mean grain size D
of crystalline structure of said copper alloy distributes in 0.3
.mu.m.ltoreq.D.ltoreq.3- .5 .mu.m; and 0.2% yield strength in
recrystallization state of said copper alloy is higher than 250
N/mm.sup.2.
2. The high strength copper alloy according to claim 1, wherein
said copper alloy contains 0.005 to 0.5 mass percent of Co, wherein
said mass percent of Co and said mass percent of Si satisfy the
relationship Co/Si=0.005 to 0.5.
3. The high strength copper alloy according to claim 1, wherein
said copper alloy contains 0.03 to 1.5 mass percent of Sn, wherein
said mass percent of Sn and said mass percent of Si satisfy the
relationship Si/Sn.gtoreq.1.5.
4. The high strength copper alloy according to claim 2, wherein
said copper alloy contains 0.03 to 1.5 mass percent of Sn, wherein
said mass percent of Sn and said mass percent of Si satisfy the
relationship Si/Sn.gtoreq.1.5.
5. The high strength copper alloy according to claim 1, wherein
said copper alloy contains 0.005 to 0.3 mass percent of Fe and/or
0.005 to 0.3 mass percent of Ni, wherein said mass percent of Fe,
said mass percent of Ni and said mass percent of Si satisfy the
relationship (Fe+Ni)/Si=0.005 to 0.5.
6. The high strength copper alloy according to claim 3, wherein
said copper alloy contains 0.005 to 0.3 mass percent of Fe and/or
0.005 to 0.3 mass percent of Ni, wherein said mass percent of Fe,
said mass percent of Ni and said mass percent of Si satisfy the
relationship (Fe+Ni)/Si=0.005 to 0.5.
7. The high strength copper alloy according to claim 2, wherein
said copper alloy contains 0.005 to 0.3 mass percent of Fe and/or
0.005 to 0.3 mass percent of Ni, wherein said mass percent of Fe,
said mass percent of Ni, said mass percent of Co and said mass
percent of Si satisfy the relationship (Fe+Ni+Co)/Si=0.005 to
0.5.
8. The high strength copper alloy according to claim 4, wherein
said copper alloy contains 0.005 to 0.3 mass percent of Fe and/or
0.005 to 0.3 mass percent of Ni, wherein said mass percent of Fe,
said mass percent of Ni, said mass percent of Co and said mass
percent of Si satisfy the relationship (Fe+Ni+Co)/Si=0.005 to
0.5.
9. A high strength copper alloy characterized in that said copper
alloy consists essentially of 4 to 17 mass percent of Zn, 0.1 to
0.8 mass percent of Si and the remaining mass percent of Cu,
wherein said mass percent of Zn and said mass percent of Si satisfy
the relationship Zn-2.5.Si=2.about.15 mass percent; mean grain size
D of crystalline structure of said copper alloy distributes in 0.3
.mu.m.ltoreq.D.ltoreq.3- .5 .mu.m; and 0.2% yield strength in
recrystallization state of said copper alloy is higher than 250
N/mm.sup.2.
10. The high strength copper alloy according to claim 9, wherein
said copper alloy contains 0.005 to 0.5 mass percent of Co, wherein
said mass percent Co and said mass percent of Si satisfy the
relationship Co/Si=0.02 to 1.5.
11. The high strength copper alloy according to claim 9, wherein
said copper alloy contains 0.2 to 3 mass percent of Sn, wherein
said mass percent of Sn and said mass percent of Si satisfy the
relationship Si/Sn.ltoreq.0.5.
12. The high strength copper alloy according to claim 10, wherein
said copper alloy contains 0.2 to 3 mass percent of Sn, wherein
said mass percent of Sn and said mass percent of Si satisfy the
relationship Si/Sn.ltoreq.0.5.
13. The high strength copper alloy according to claim 9, wherein
said copper alloy contains 0.005 to 0.3 mass percent of Fe and/or
0.005 to 0.3 mass percent of Ni, wherein said mass percent of Fe,
said mass percent of Ni and said mass percent of Si satisfy the
relationship (Fe+Ni)/Si=0.02 to 1.5.
14. The high strength copper alloy according to claim 11, wherein
said copper alloy contains 0.005 to 0.3 mass percent of Fe and/or
0.005 to 0.3 mass percent of Ni, wherein said mass percent Fe, said
mass percent of Ni and said mass percent of Si satisfy the
relationship (Fe+Ni)/Si=0.02 to 1.5.
15. The high strength copper alloy according to claim 10, wherein
said copper alloy contains 0.005 to 0.3 mass percent of Fe and/or
0.005 to 0.3 mass percent of Ni, wherein said mass percent of Fe,
said mass percent of Ni, said mass percent of Co and said mass
percent of Si satisfy the relationship (Fe+Ni+Co)/Si=0.02 to
1.5.
16. The high strength copper alloy according to claim 12, wherein
said copper alloy contains 0.005 to 0.3 mass percent of Fe and/or
0.005 to 0.3 mass percent of Ni, wherein said mass percent of Fe,
said mass percent of Ni, said mass percent of Co and said mass
percent of Si satisfy the relationship (Fe+Ni+Co)/Si=0.02 to
1.5.
17. The high strength copper alloy according to any one of claims 1
through 16, wherein said copper alloy contains at least one element
selected from a group of P, Sb, As, Sr, Mg, Y, Cr, La, Ti, Mn, Zr,
In and Hf, wherein content of said element is 0.003 to 0.3 mass
percent.
18. A high strength copper alloy characterized in that said copper
alloy consists essentially of 66 to 76 mass percent of Cu, 21 to 33
mass percent of Zn and 0.5 to 2 mass percent of Si and the
remaining mass percent of Cu, wherein said mass percent of Cu, said
mass percent of Zn and said mass percent of Si satisfy the
relationship Cu-5.Si=62 to 67 mass percent and Zn+6.Si=32 to 38
mass percent; mean grain size D of crystalline structure of said
copper alloy distributes in 0.3 .mu.m.ltoreq.D.ltoreq.3.5 .mu.m;
and 0.2% yield strength in recrystallization state of said copper
alloy is higher than 250 N/mm.sup.2.
19. The high strength copper alloy according to claim 18, wherein
said copper alloy contains 0.005 to 0.3 mass percent of Co, wherein
said mass percent of Co and said mass percent of Si satisfy the
relationship Co/Si=0.005 to 0.4.
20. The high strength copper alloy according to claim 18, wherein
said copper alloy contains 0.03 to 1 mass percent of Sn, wherein
said mass percent of Si and said mass percent of Sn satisfy the
relationship Si/Sn.gtoreq.1.
21. The high strength copper alloy according to claim 19, wherein
said copper alloy contains 0.03 to 1 mass percent of Sn, wherein
said mass percent of Si and said mass percent of Sn satisfy the
relationship Si/Sn.gtoreq.1.
22. The high strength copper alloy according to claim 18, wherein
said copper alloy contains 0.005 to 0.3 mass percent of Fe and/or
0.005 to 0.3 mass percent of Ni, wherein said mass percent of Fe,
said mass percent of Ni and said mass percent of Si satisfy the
relationship (Fe+Ni)/Si=0.005 to 0.4.
23. The high strength copper alloy according to claim 20, wherein
said copper alloy contains 0.005 to 0.3 mass percent of Fe and/or
0.005 to 0.3 mass percent of Ni, wherein said mass percent of Fe,
said mass percent of Ni and said mass percent of Si satisfy the
relationship (Fe+Ni)/Si=0.005 to 0.4.
24. The high strength copper alloy according to claim 19, wherein
said copper alloy contains 0.005 to 0.3 mass percent of Fe and/or
0.005 to 0.3 mass percent of Ni, wherein said mass percent of Fe,
said mass percent of Ni, said mass percent of Co and said mass
percent of Si satisfy the relationship (Fe+Ni+Co)/Si=0.005 to
0.4.
25. The high strength copper alloy according to claim 21, wherein
said copper alloy contains 0.005 to 0.3 mass percent of Fe and/or
0.005 to 0.3 mass percent of Ni, wherein said mass percent of Fe,
said mass percent of Ni, said mass percent of Co and said mass
percent of Si satisfy the relationship (Fe+Ni+Co)/Si=0.005 to
0.4.
26. The high strength copper alloy according to any one of claims
18 through 25, wherein said copper alloy contains at least one
element selected from a group of P, Sb, As, Sr, Mg, Y, Cr, La, Ti,
Mn, Zr, In and Hf, wherein content of P, Sb, or As is 0.005 to 0.3
mass percent, content of Sr, Mg, Y, Cr, La, Ti, Mn, Zr, In or Hf is
0.003 to 0.3 mass percent, and total content in a case selected
from at least P, Sb or As is 0.005 to 0.25 mass percent.
27. The high strength copper alloy according to any one of claims 1
through 26, wherein said copper alloy is recrystallized material
obtained from recrystallization of plastic working blank, which is
formed by plastic working including cold working with working rate
being more than 30 percent.
28. The high strength copper alloy according to claim 27, wherein
said recrystallized materials are obtained by heat-treatment of
said plastic working blank at the range from 450 to 750.degree. C.
for 1 to 1000 seconds.
29. The high strength copper alloy according to claim 27, wherein
said cold working materials are obtained by cold rolling works or
cold wire drawing of said recrystallized materials.
30. The high strength copper alloy according to claim 29, wherein
said copper alloy is obtained by heat-treatment of said cold
working materials at the range from 150 to 600.degree. C. for 1
second to 4 hours.
31. The high strength copper alloy according to claim 29, wherein
said copper alloys are manufactured pieces obtained by working said
cold working materials to a predetermined form.
32. The high strength copper alloy according to claim 31, wherein
said copper alloy is obtained by heat-treatment of said cold
working materials at the range from 150 to 600.degree. C. for 1
second to 4 hours.
33. The high strength copper alloy according to any one of claims 1
through 17, wherein said copper alloy is rolled material or
manufactured piece with a predetermined form obtained by working
said rolled material.
34. The high strength copper alloy according to any one of claims
18 through 26, wherein said copper alloys are wire drawing material
or manufactured pieces with a predetermined form obtained by
working said wire drawing material.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to the high strength copper
alloy suitable for materials comprising leads, switches,
connectors, relays and sliding pieces etc. which are parts of
electrical devices, electronic devices, communication equipments,
information appliances, measuring instruments, automobiles and so
on.
[0003] 2. Prior Art
[0004] In general, high strength copper alloys are used as
materials comprising leads, switches, connectors, relays and
sliding pieces etc., which are used as parts of electrical devices,
electronic devices, and communication devices, information
appliances, measuring instruments, automobiles, and so on.
Recently, their devices have been improved toward miniaturization,
lightweighting, and higher efficiency, so that there are extremely
severe demands for the improvements of characteristics of the
materials. For example, the extremely thin plates are employed for
the spring contact member of the connector. The higher strength is
required for the high strength copper alloy comprising said
extremely thin plates in order to thin the plate still more. It is
also demanded for the high strength copper alloy to have higher
balance between the strength and ductility including the bending
characteristics, superiority in productivity and economy without
problems of conductivity, stress relaxation characteristic,
soldering characteristics, abrasion resistance, and corrosion
resistance such as stress corrosion cracking resistance,
dezincification corrosion resistance and migration resistance.
[0005] Incidentally, beryllium copper, titanium copper, aluminum
bronze, phosphor bronze, nickel silver, brass and brass doped with
Sn or Ni are generally well-known for the high strength copper
alloys. However, there are following problems for these high
strength copper alloys, so that it was impossible to satisfy the
above demands.
[0006] The beryllium copper has the highest strength in the copper
alloys, but the beryllium is extremely harmful to the humans: in
particular the beryllium vapor in fusion state is significantly
dangerous for the humans even in a very small amount, so that
initial cost of melting arrangement becomes extremely expensive
because of difficulty in disposal processes, particularly in a
firing treatment of the beryllium copper materials or their
products. Therefore, the melting process becomes necessary at the
last step of manufacturing to obtain the predetermined
characteristics, and then the problems appear in economy including
the manufacturing cost.
[0007] In addition, the titanium copper shows the higher strength
to next to beryllium copper, but the expensive melting arrangement
is required because titanium is active element, and hence it
becomes difficult to keep quality and yield in the melting. As well
as the beryllium copper, since the melting process becomes
necessary at the last step of manufacturing, the problems in
economy appear.
[0008] For the aluminum bronze, it is difficult to obtain pure
ingots because aluminum is an active element, and furthermore the
aluminum bronze has the lower soldering characteristics.
[0009] Moreover, as the phosphor bronze and the nickel silver have
the lower hot workability, it is difficult to produce them by hot
rolling. Their alloys are usually produced with horizontal
continuous casting. Consequently, their alloys are inferior in the
productivity, the yield and the energy cost. Additionally, as to a
spring phosphor-bronze and a spring nickel-silver which are
representative copper alloys with high strength, problems in
economy appear because expensive Sn and Ni are abundantly contained
in the two alloys.
[0010] The brass or brass doped with Si and Ni is inexpensive, but
there are problems with respect to the corrosion resistance such as
the stress corrosion cracking and dezincification, and then they
are unsuitable for the parts to realize miniaturization and higher
efficiency.
[0011] As a result, these conventional high strength copper alloys
are not satisfied as the parts used in the various devices with
tendency toward miniaturization, lightweighting and higher
efficiency, so that the development of a new high strength copper
alloy is demanded greatly.
SUMMARY OF THE INVENTION
[0012] Present inventors have paid their attention to the
Hall-Petch relationship (E. O. Hall, Proc. Phys. Soc. London. 64
(1951) 747. and N. J. Petch, J. Iron Steel Inst. 174 (1953) 25.)
that 0.2% proof stress is proportional to grain size (D.sup.-1/2),
where said 0.2% proof stress is defined by the strength that
permanent strain becomes 0.2%, and said 0.2% proof stress is
sometimes abbreviated as "proof stress". The present inventors have
considered that the high strength copper alloys satisfying the
demands of said epoch can be obtained by grain refinement, and then
several investigations and experiments have been performed on the
grain refinement. From their results, it is found that the
micronization for the crystal grain (grain refinement) of the
copper alloys is realized by selecting suitably additive elements
in the recrystallization. It is recognized that the strength
including mainly the 0.2% proof stress is improved remarkably by
making the crystal grain size smaller than a certain size and its
strength also increases with decreasing of the grain size.
Furthermore, from the results of various experiments with respect
to influence of the additive elements for micronization of the
grain size, it is clarified that addition of Si to Cu--Zn alloy
increases the number of nucleation sites and addition of Co to
Cu--Zn--Si alloy suppresses the grain growth. This means that
Cu--Zn--Si or Cu--Zn--Si--Co alloy system with fine grains is
obtained by exploiting their effects. In other words, the increase
of nucleation sites is considered to be due to decreasing of
stacking fault energy based on the addition of Si, and the
suppression of the grain growth is considered to be due to the
formation of fine precipitates based on the addition of Co.
[0013] The present invention is completed based upon these
investigated results and relates to new high strength copper alloy
superior in mechanical properties, workability and corrosion
resistance without problems in economy. In particular the invention
is suitable for materials of the parts composing several devices in
tendency of miniaturization, lightweighting and higher efficiency.
Accordingly, it is the object of the present invention to provide
new high strength copper alloy that is extensively applied and
extremely rich in utility.
[0014] Namely, it is mainly first object of the present invention
to provide the high strength copper alloy (called "first invention
copper alloy") suitable for rolled stocks (plates, rods and wires
etc.) required high strength, or the work piece of rolled stock
(press-forming product and bending product etc.), and this alloy is
in the following. In addition, as parts and products suitably
manufactured by use of first invention copper alloy, there are the
portable or miniature communication equipments which are required
thinization (to thin the plate still more) and lightweighting,
electronic device parts used for personal computer, medical care
instrument parts, accessory parts, machine parts, tubes or plates
of heat exchanger, cooling instruments using sea water, parts
composing inlet or outlet of sea water in small size ship, wiring
tool parts, various instrument parts for automobile,
measuring-instrument parts, play tools and daily necessities and so
on. There are concretely connectors, relays, switches, sockets,
springs, gears, pins, washers, coins for play, keys, tumblers,
buttons, hooks, braces, diaphragms, bellows, sliding pieces,
bearings, sliding pieces adjusting sound volume, bushes, fuse
grips, lead frames and gauge board and so on.
[0015] It is mainly second object of the present invention to
provide the high strength copper alloy (called "second invention
copper alloy") suitable for rolled stocks (plates, rods and wires
etc.) required highly balanced strength and electric conductivity,
or the work piece of rolled stock (press-forming product and
bending product etc.), where the strength required for first
invention copper alloy is not needed. In addition, as parts and
products suitably manufactured by use of second invention copper
alloy, there are electronic device parts required electric
conductivity, measuring-instrument parts, household electric
appliance parts, tubes or plates of heat exchanger, cooling
instruments using sea water, parts composing inlet or outlet of sea
water in small size ship, machine parts, play tools and daily
necessities and so on. There are concretely connectors, switches,
relays, bushes, fuse grips, lead frames, wiring instruments, keys,
tumblers, buttons, hooks, braces, diaphragms, bellows, sliding
pieces, bearings, coins for play, and so on.
[0016] Furthermore, it is mainly third object of the present
invention to provide the high strength copper alloy (called "third
invention copper alloy") suitable for wire drawing materials
[general wire material of round cross section and deformed wire
material such as rectangle cross section (square etc.), polygon
cross section (hexagon etc.) and so on] or the workpiece of wire
drawing materials (bending product etc.), where the strength
required for first invention copper alloy is needed. In addition,
as parts and products suitably manufactured by use of third
invention copper alloy, there are electronic device parts, parts
for construction, accessory parts, machine parts, play tools,
various instrument parts for automobile, measuring-instrument
parts, electronic device parts and electrical device parts. There
are concretely connectors, keys, header members, nails (nails for
play instrument), washers, pins, screws, coiled springs, lead
screws, shafts of copying machines etc., wire gauzes (wire gauze
for culture or filter for inlet and outlet of seawater used in
seawater cooling equipment and small ship etc.), sliding pieces,
bearings, bolts and so on.
[0017] The first invention copper alloy consists essentially of 4
to 19 mass percent (preferably 6 to 15 mass percent, more
preferably 7 to 13 mass percent) of Zn, 0.5 to 2.5 mass percent
(preferably 0.9 to 2.3 mass percent, more preferably 1.3 to 2.2
mass percent)of Si and the remaining mass percent of Cu, wherein
said mass percent of Zn and said mass percent of Si satisfy the
relationship Zn-2.5.Si=0 to 15 mass percent (preferably 1 to 12
mass percent, more preferably 2 to 9 mass percent); mean grain size
D of crystalline structure of said copper alloy distributes in 0.3
.mu.m.ltoreq.D.ltoreq.3.5 .mu.m (preferably 0.3
.mu.m.ltoreq.D.ltoreq.2.5 .mu.m, more preferably 0.3
.mu.m.ltoreq.D.ltoreq.2 .mu.m); and 0.2% proof stress in
recrystallization state of said copper alloy is higher than 250
N/mm.sup.2 (preferably higher than 300 N/mm.sup.2).
[0018] In addition, the second invention copper alloy consists
essentially of 4 to 17 mass percent (preferably 5 to 13 mass
percent, more preferably 6 to 11.5 mass percent) of Zn, 0.1 to 0.8
mass percent (preferably 0.2 to 0.6 mass percent, more preferably
0.2 to 0.5 mass percent) of Si and the remaining mass percent of
Cu, wherein said mass percent of Zn and said mass percent of Si
satisfy the relationship Zn-2.5.Si=2 to 15 mass percent (preferably
4 to 12 mass percent, more preferably 5 to 10 mass percent); mean
grain size D of crystalline structure of said copper alloy
distributes in 0.3 .mu.m.ltoreq.D.ltoreq.3.5 .mu.m (preferably 0.3
.mu.m.ltoreq.D.ltoreq.3 .mu.m, more preferably 0.3
.mu.m.ltoreq.D.ltoreq.2.5 .mu.m); and 0.2% proof stress in
recrystallization state of said copper alloy is higher than 250
N/mm.sup.2 (preferably higher than 300 N/mm.sup.2).
[0019] Furthermore, the third invention copper alloy consists
essentially of 66 to 76 mass percent (preferably 68 to 75.5 mass
percent) of Cu, 21 to 33 mass percent (preferably 22 to 31 mass
percent) of Zn and 0.5 to 2 mass percent (preferably 0.8 to 1.8
mass percent, more preferably 1 to 1.7 mass percent) of Si, wherein
said mass percent of Cu, said mass percent of Zn and said mass
percent of Si satisfy the relationships Cu-5.Si=62 to 67
(preferably Cu-5.Si=63 to 66.5 mass percent) and Zn+6.Si=32 to 38
(preferably Zn+6.Si=33 to 37 mass percent); mean grain size D of
crystalline structure of said copper alloy distributes in 0.3
.mu.m.ltoreq.D.ltoreq.3.5 .mu.m(preferably 0.3
.mu.m.ltoreq.D.ltoreq.3 .mu.m, more preferably 0.3
.mu.m.ltoreq.D.ltoreq.2.5 .mu.m); and 0.2% proof stress in
recrystallization state of said copper alloy is higher than 250
N/mm.sup.2 (preferably higher than 300 N/mm.sup.2).
[0020] In order to obtain said each invention copper alloy, there
are some cases receiving a plurality of recrystallization
treatments in which a part or all of the alloy structure is
recrystallized by the heat treatment. In such cases, said mean
grain size D and said 0.2% proof stress in copper alloy are
determined from said two physical quantities of the materials
(called "recrystallization materials") obtained from the
recrystallization treatment performed at last (called "last
recrystallization treatment"). In the case that said
recrystallization treatment is performed only once, it goes without
saying that the recrystallization treatment is the last
recrystallization treatment and the treated materials are the
recrystallization materials.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0021] Each invention copper alloy is provided with any form shown
in the following preferred embodiments.
Embodiment 1
[0022] Ingots are worked into plastic working blanks with
predetermined forms by the plastic working including the hot
working (rolling, extruding and forging etc.) and/or the cold
working (rolling and wire drawing etc.). The plastic working blanks
receive the recrystallization treatment (last recrystallization
treatment) based upon heat treatment (annealing etc.) in the range
of the recrystallization temperature, and then become the
recrystallization materials. The recrystallization materials are
rolled stocks in first and second invention copper alloys, and wire
drawing materials in third invention copper alloy.
Embodiment 2
[0023] The recrystallization materials of said embodiment 1 are
worked into the cold working materials with predetermined forms
according to cold working (rolling, wire drawing and forging). The
cold working materials are rolled stocks in first and second
invention copper alloys, and wire drawing materials in third
invention copper alloy.
Embodiment 3
[0024] The recrystallization materials of said embodiment 1 are
worked into manufacture pieces with predetermined forms according
to press working or bending etc.
Embodiment 4
[0025] The cold working materials of said embodiment 2 are worked
into manufacture pieces with predetermined forms according to press
working or bending etc.
[0026] In order to improve the property of first invention copper
alloy, it is desired for the copper alloy composition to contain
0.005 to 0.5 mass percent (preferably 0.01 to 0.3 mass percent,
more preferably 0.02 to 0.2 mass percent) of Co and/or 0.03 to 1.5
mass percent (preferably 0.05 to 0.7 mass percent, more preferably
0.05 to 0.5 mass percent) of Sn.
[0027] In this case, the contents of Co and Sn are determined from
said each range under consideration of the content of Si. In other
words, the content of Co is determined to satisfy the relationship
Co/Si=0.05 to 0.5 (preferably Co/Si=0.01 to 0.3, more preferably
Co/Si=0.03 to 0.2), wherein the value of Co content divided by Si
content is defined by Co/Si. Additionally, the content of Sn is
determined to satisfy the relationship Si/Sn.gtoreq.1.5 (preferably
Si/Sn.gtoreq.2, more preferably Si/Sn.gtoreq.3), wherein the value
of Si content divided by Sn content is defined by Si/Sn.
[0028] In first invention copper alloy, it is possible for the
copper alloy composition to contain 0.005 to 0.3 mass percent
(preferably 0.01 to 0.2 mass percent) of Fe and/or 0.005 to 0.3
mass percent (preferably 0.01 to 0.2 mass percent) of Ni in
substitution for Co or together with Co.
[0029] For said composition, the content of Fe or Ni is determined
under consideration of the content of Si. In the case added with
Co, the contents of Si and Co are considered. Namely, the content
of Fe or Ni is determined to satisfy the relationship
(Fe+Ni+Co)/Si=0.005 to 0.5 (preferably (Fe+Ni+Co)/Si=0.01 to 0.3,
more preferably (Fe+Ni+Co)/Si=0.03 to 0.2), wherein the value of
total contents containing Co divided by Si content is defined by
(Fe+Ni+Co)/Si. It is desirable for such determination that said
total content (Fe+Ni+Co) is adjusted to be 0.005 to 0.55 mass
percent (more preferably 0.01 to 0.35 mass percent, much more
preferably 0.02 to 0.2 mass percent).
[0030] In order to improve the characteristics more in second
invention copper alloy, it is preferable to contain Co of 0.005 to
0.5 mass percent (preferably 0.01 to 0.3 mass percent, more
preferably 0.02 to 0.2 mass percent) and/or Sn of 0.2 to 3 mass
percent (preferably 1 to 2.6 mass percent, more preferably 1.2 to
2.5 mass percent) in alloy composition. In this case, the contents
of Co and Sn are determined by considering the relation to Si
content. In other words, the content of Co is determined to satisfy
the relationship Co/Si=0.02 to 1.5 (preferably Co/Si=0.04 to 1,
more preferably Co/Si=0.06 to 0.5) in the range described above. In
addition, the content of Sn is determined to satisfy the
relationship Si/Sn.ltoreq.0.5 (preferably Si/Sn.ltoreq.0.4, more
preferably Si/Sn.ltoreq.0.3) in the range described above.
[0031] In second invention copper alloy, it is possible to contain
Fe of 0.005 to 0.3 mass percent (preferably 0.01 to 0.2 mass
percent) and/or Ni of 0.005 to 0.3 mass percent (preferably 0.01 to
0.2 mass percent) in substitution for Co or together with Co. In
this case, the content of Fe or Ni is determined by considering the
content of Si (or both contents of Si and Co in case of co-adding
Co). In other words, the contents of Fe and Ni are determined to
satisfy the relationship (Fe+Ni+Co)/Si=0.02 to 1.5 (preferably
(Fe+Ni+Co)/Si=0.04 to 1, more preferably (Fe+Ni+Co)/Si=0.06 to
0.5). It is desirable for such determination that said total
content (Fe+Ni+Co) is adjusted to be 0.005 to 0.55 mass percent
(preferably 0.01 to 0.35 mass percent, more preferably 0.02 to 0.25
mass percent).
[0032] Furthermore, for the first and second invention copper
alloys, it is possible to contain at least one element selected
from a group of P, Sb, As, Sr, Mg, Y, Cr, La, Ti, Mn, Zr, In and Hf
corresponding to characteristics required in their applications.
The contents of these elements are determined appropriately in the
range of 0.003 to 0.3 mass percent.
[0033] In order to improve the characteristics of third invention
copper alloy, it is preferable to contain Co of 0.005 to 0.3 mass
percent (preferably 0.01 to 0.2 mass percent, more preferably 0.02
to 0.15 mass percent) and/or Sn of 0.03 to 1 mass percent
(preferably 0.05 to 0.7 mass percent, more preferably 0.05 to 0.5
mass percent) in alloy composition.
[0034] In this case, the contents of Co and Sn are determined by
considering the content of Si in above range. In other words, the
content of Co is determined to satisfy the relationship Co/Si=0.005
to 0.4 (preferably Co/Si=0.01 to 0.2, more preferably Co/Si=0.02 to
0.15). In addition, the content of Sn is determined to satisfy the
relationship Si/Sn.gtoreq.1 (preferably Si/Sn.gtoreq.1.5, more
preferably Si/Sn.gtoreq.2).
[0035] For the third invention copper alloy, it is possible to
contain Fe of 0.005 to 0.3 mass percent (preferably 0.01 to 0.2
mass percent) and/or Ni of 0.005 to 0.3 mass percent (preferably
0.01 to 0.2 mass percent) in substitution for Co or together with
Co.
[0036] In this case, the content of Fe or Ni is determined by
considering the content of Si (or both contents of Si and Co in
case of co-adding Co). In other words, the contents of Fe and Ni
are determined to satisfy the relationship (Fe+Ni+Co)/Si=0.005 to
0.4 (preferably (Fe+Ni+Co)/Si=0.01 to 0.2, more preferably
(Fe+Ni+Co)/Si=0.02 to 0.15). It is desirable for such determination
that said total content (Fe+Ni+Co) is adjusted to be 0.005 to 0.35
mass percent (more preferably 0.01 to 0.25 mass percent, much more
preferably 0.02 to 0.2 mass percent).
[0037] Furthermore, in alloy composition for third invention copper
alloy, it is possible to contain at least one element selected from
a group of P, Sb, As, Sr, Mg, Y, Cr, La, Ti, Mn, Zr, In and Hf
corresponding to characteristics required in their applications,
where each content of P, Sb, or As is 0.005 to 0.3 mass percent and
each content of Sr, Mg, Y, Cr, La, Ti, Mn, Zr, In or Hf is 0.003 to
0.3 mass percent, and the total content in cases selecting at least
one element from P, Sb and As is 0.005 to 0.25 mass percent.
[0038] By the way, the strength, particularly the 0.2% proof
stress, is enhanced by the grain (recrystallized grain) refinement.
The present inventors have confirmed experimentally that the 0.2%
proof stress is enhanced remarkably for the mean grain size less
than 3.5 .mu.m in comparison with the case larger than 3.5 .mu.m.
In addition, by reducing gradually the mean grain size D from 3.5
.mu.m, it is identified that the enhanced ratio of the proof stress
increase rapidly at 3, 2.5 and 2 .mu.m. From such experimental
results, it is found that the proof stress (generally higher than
250 N/mm.sup.2, preferably higher than 300 N/mm.sup.2) required for
the parts of the electrical devices, electronic devices,
communication equipments and measuring instruments is ensured in
the mean grain size D less than 3.5 .mu.m. In the case demanding
high strength (the proof stress), it is preferable for mean grain
size D to be less than 3.0 cm, and in the case demanding higher
strength, it is preferable to be less than 2.5 .mu.m. In order to
improve rapidly the strength in the possible range, it is
preferable for mean grain size D to be less than 2 .mu.m. On the
other hand, although the proof stress is improved with decrease of
the mean grain size D, it is predictably difficult to obtain
practically grains less than 0.3 .mu.m because the smallest grain
size confirmed by the experiments is 0.3 .mu.m.
[0039] From such points, in order to ensure the proof stress higher
than 250 N/mm.sup.2 (preferably higher than 300 N/mm.sup.2) in the
first, second and third invention copper alloys, the recrystallized
structure of 0.3 .mu.m.ltoreq.D.ltoreq.3.5 mm is required. In other
words, it is necessary that the mean grain size D in the
recrystallization state (state after the last recrystallization
treatment) distributes in 0.3 .mu.m.ltoreq.D.ltoreq.3.5 .mu.m and
0.2% proof stress is higher than 250 N/mm.sup.2. In the case
demanding the higher strength for the second and third invention
copper alloys, it is preferable to distribute in 0.3
.mu.m.ltoreq.D.ltoreq.3 .mu.m, and more preferable to distribute in
0.3 .mu.m.ltoreq.D.ltoreq.2.5 .mu.m. On the other hand, in the
first invention copper alloy required sometimes the strength higher
than the second and third invention copper alloys, it is preferable
to distribute in 0.3 .mu.m.ltoreq.D.ltoreq.2.5 .mu.m, and more
preferable to distribute in 0.3 .mu.m.ltoreq.D.ltoreq.2 .mu.m.
[0040] Additionally, in the first to third invention copper alloys
of which grain refinement is realized by recrystallization due to
the suitable heat-treatment (generally annealing), such grain
refinement becomes possible in alloy composition described
above.
[0041] Namely, in the first to third invention copper alloys, Zn
and Si cause the stacking fault energy to decrease, the dislocation
density to increase, and the nucleus sites of recrystallized grain
generation to increase. The functions which contributes to the
grain refinement and the material strengthening due to solid
solution into the Cu matrix (both functions are called "grain
refinement and strengthening" as following) are given, and the
contents of those elements are determined by said ranges as
mentioned below. In other words, for first and second invention
copper alloys used mainly as the rolled stocks or the manufacture
pieces, when the functions of grain refinement and strengthening
due to the addition of Zn appear enough, the content of Zn is more
than 4 mass percent, and in order to improve largely the strength
in first invention copper alloy, it is required that the content is
more than 6 mass percent (preferably higher than 7 mass percent).
For second invention copper alloy of which strength is allowed to
be inferior to the first invention, it is preferable that the
content is more than 5 mass percent (more preferably higher than 6
mass percent). On the other hand, when the content of Zn becomes
excessively, the sensitivity of the stress-corrosion cracking
increases and the bending characteristic deteriorates. Accordingly,
when the relation of the content of Si for the applications of the
rolled stock and the inhibition function of the stress corrosion
cracking is taken into consideration, the content of Zn in the
first invention copper alloy is less than 19 mass percent
(preferably less than 15 mass percent, more preferably less than 13
mass percent), and the content in the second invention copper alloy
is less than 17 mass percent (preferably less than 13 mass percent,
more preferably less than 11.5 mass percent).
[0042] On the other hand, although the grain refinement and
strengthening functions due to addition of Si appear remarkably in
pretty little quantity comparing with Zn, the functions are caused
by interaction with Zn. In addition, Si improves the
characteristics of the stress-corrosion cracking by co-addition of
Zn. However, the surplus addition of Si decreases the electric
conductivity of this alloy. When these points are taken into
consideration, it is required that the content of Si is higher than
0.5 mass percent for first invention copper alloy which
accomplishes the strength improvement and grain refinement. The
more or much more preferable content is more than 0.9 or 1.3 mass
percent, respectively. However, the electric conductivity, hot
workability and cold workability in first invention copper alloy
are decreased by the Si content (also called the content of Si) in
excess over 2.5 mass percent, and in order to keep those
characteristics enough, it is preferable that the Si content is
less than 2.3 mass percent, and the more preferable content is less
than 2.2 mass percent. On the other hand, in second invention
copper alloy that thinks the balance between the strength and the
electric conductivity important, in order to realize the
grain-refinement effect required for the predetermined strength,
the Si content of 0.1 mass percent at least is necessary, and it is
preferable to be higher than 0.2 mass percent. However, in order to
ensure the predetermined electric conductivity considering balance
with strength, it is required that the Si content is less than 0.8
mass percent, and in order to ensure the electric conductivity
enough to be used for the applications, it is preferable to be less
than 0.6 mass percent (more preferably less than 0.5 mass
percent).
[0043] Furthermore, in first and second invention copper alloys, it
is necessary that balance among the effect of grain refinement,
stress-corrosion cracking characteristics and the strength is kept
by the co-addition of Zn and Si, but it is unsuitable in these
alloys to determine independently the individual content in said
range. Accordingly, it is necessary that the relation of the Zn and
Si contents is specified by the relationship Zn-2.5.Si and the
values of this formulae are determined to be in above predetermined
range. In order to obtain the predetermined strength based upon the
grain refinement, it is necessary for first invention copper alloy
to satisfy the relationship Zn-2.5.Si.gtoreq.0 mass percent, and
the preferable relationship is Zn-2.5.Si.gtoreq.1 mass percent
(more preferably Zn-2.5.Si.gtoreq.2 mass percent ), and it is
necessary for second invention copper alloy to satisfy the
relationship Zn-2.5.Si.gtoreq.2 mass percent, and the preferable
relationship is Zn-2.5.Si.gtoreq.4 mass percent (more preferably
Zn-2.5.Si.gtoreq.5 mass percent ). On the other hand, in any of
first and second invention copper alloys, it is necessary to
satisfy the relationship Zn-2.5.Si.gtoreq.15 mass percent because
the stress corrosion cracking arises remarkably for Zn-2.5.Si>15
mass percent. In order to inhibit effectively the stress corrosion
cracking, it is preferable to satisfy the relationship
Zn-2.5.Si.ltoreq.12 mass percent (more preferably
Zn-2.5.Si.ltoreq.9 mass percent for first invention copper alloy,
and Zn-2.5.Si.ltoreq.10 mass percent for second invention copper
alloy).
[0044] In addition, for the Zn content in third invention copper
alloy, the grain refinement and strength are rightly considered as
well as first and second invention copper alloys. Furthermore,
since the third invention copper alloy is mainly used as wire
drawing material and its manufactured piece, the Zn content should
be determined in consideration of hot extruding characteristics, so
that the Zn content is set to be abundantly in comparison with
first and second invention copper alloys. In order to ensure the
hot extruding characteristics enough, it is necessary for Zn
content to be higher than 21 mass percent. It is more preferable
for Zn content to be higher than 22 mass percent so that hot
extruding-wire drawing can be kept more excellent. Although the
characteristics of stress-corrosion cracking resistance of third
invention copper alloy is inferior in comparison with first and
second invention copper alloys, this characteristics can be
satisfied enough for use of wire etc. because Zn content is a
little in comparison with general Cu--Zn system alloy (for example,
JIS-C2700 (65Cu-35Zn)). However, in order to ensure enough the
stress-corrosion cracking resistance and cold workability, it is
required that Zn content of third invention copper alloy is lower
than 33 mass percent. In other words, when Zn content is higher
than 33 mass percent, .beta. and .gamma. phases are easy to remain
and give a wrong influence upon the cold workability. Furthermore,
the stress corrosion cracking resistance and dezincification
corrosion become also problems. In order to carry out the hot
extrusion-wire drawing well while the stress corrosion cracking
resistance and the cold workability are ensured, it is preferable
for Zn content to be less than 31 mass percent. In order to ensure
the hot extrusion characteristics and the cold workability, it is
necessary in third invention copper alloy to consider the Cu
content, and the .beta. and .gamma. phases are easy to remain when
the Cu content is less than 66 mass percent. On the other hand,
when the content is higher than 76 mass percent, it gets difficult
to perform the hot extrusion. Therefore, it is necessary for the Cu
content to be 66 to 76 mass percent. Furthermore, in order to
ensure the cold workability and the hot extrusion characteristics
enough, it is preferable to be 68 to 75.5 mass percent.
[0045] In addition, as mentioned above, Si shows the grain
refinement, strength improvement and inhibition function of
stress-corrosion cracking by adding together with Zn. Accordingly,
in the case that the grain refinement and strength improvement are
the principal object of third invention copper alloy used as wire
drawing material, it is necessary for the content of Si to be
higher than 0.5 mass percent as well as first invention copper
alloy. Considering that said copper alloy is utilized as wire
drawing material, it is preferable to be higher than 0.8 mass
percent and the most preferable to be higher than 1 mass percent.
However, when the Si content becomes higher than 2 mass percent,
the .gamma. or .beta. phase which is a factor obstructing cold
workability precipitate. Therefore, it is required to be less than
2 mass percent so that the cold workability is ensured, and if
considering that plenty of Zn is added, it is preferable to be less
than 1.8 mass percent, and more preferable to be less than 1.7 mass
percent.
[0046] Furthermore, in order to ensure the hot extrusion
characteristics, cold workability and stress corrosion cracking
resistance in third invention copper alloy, it is unsuitable that
the individual contents of Cu, Si and Zn are determined
independently. Namely, it is necessary that the contents of Cu, Si
and Zn are determined so as to satisfy the relationship Cu-5.Si=62
to 67 mass percent and Zn-6.Si=32 to 38 mass percent. In other
words, even though the contents of Cu, Si and Zn are in said range,
the preferable hot workability can not be ensured when the contents
of Cu, Si and Zn satisfy the relationships Cu-5.Si>67 mass
percent or Zn+6.Si<32 mass percent. On the other hands, when
Cu-5.Si<62 mass percent or Zn+6.Si>38, the cold workability
worsens because concentrations of Zn and Si at grain boundary
become higher, and .beta. and .gamma. phases became easy to remain.
Additionally, it becomes easy for the stress corrosion cracking to
appear, and for some applications, problems of dezincification
corrosion are also caused easily. In order to ensure enough the
cold workability and stress-corrosion cracking resistance without
these problems, it is preferable that the contents of Cu, Si and Zn
are determined to satisfy the relationships Cu-5.Si=63 to 66.5 mass
percent and Zn+6.Si=33 to 37 mass percent.
[0047] Incidentally, the grains grow with the rise of temperature
or with time, and then in the recrystallization process, the whole
of grains does not recrystallize at the same time and the parts
easy to recrystallize start to recrystallize at first and a long
time becomes necessary until its recrystallization finish in all
structures. Therefore, the crystal grains recrystallizing at the
initial stage of the recrystalization process continue to grow till
the recrystallization process finishes, and then the crystal grains
become considerably large at the time point that all structures
have recrystallized completely. Consequently, it is preferable to
inhibit growth of recrystallized grains in the recrystallization,
so that the fine recrystallized grains distribute uniformly in all
structures. Co has a function inhibiting growth of the
recrystallized grains, and this is the reason of Co addition in
first to third invention copper alloys. In other words, Co combines
with Si, and the growth of crystal grains is suppressed by forming
fine precipitates (Co2Si of about 0.01 .mu.m, etc.). In order that
the Co shows the function inhibiting the growth of crystal grain,
it is necessary for the Co content to be higher than 0.005 mass
percent. All of the added Co is not concerned with formation of
said precipitate but the solid solution part of Co improves the
heat resistance of matrix and stress relaxation characteristic.
Accordingly, in order that such functions improving stress
relaxation characteristic and heat resistance are shown enough, it
is preferable for all copper alloys of first to third inventions to
be higher than 0.01 mass percent, and it is more preferable to be
higher than 0.02 mass percent. On the other hands, when the Co
addition becomes higher than 0.5 mass percent or 0.3 mass percent
in the first and second invention copper alloys, and the third
invention copper alloy, respectively, it is difficult to improve
still more the effect of grain-growth inhibition and the
improvement effect of stress relaxation characteristic needed in
applications because of those saturation, and then it is useless
economically. Furthermore, there is a possibility that such
additions lower the bending characteristics because of enlarging of
precipitating particle and increasing of precipitating amount.
Therefore, it is necessary for content of Co in the first and
second invention copper alloys to be lower than 0.5 mass percent
and for content of Co in the third invention copper alloy to be
lower than 0.3 mass percent. However, in order to show effectively
said functions and to ensure bending characteristics enough, it is
preferable that the contents of Co in the first and second
invention copper alloys become less than 0.3 mass percent, and it
is more preferable that the contents become less than 0.2 mass
percent. From the same reasons, it is preferable that the content
of Co in the third invention copper alloy becomes less than 0.2
mass percent, and it is more preferable that the content becomes
less than 0.15 mass percent.
[0048] In addition, since Co have the close relation with Si in the
grain refinement, the content of Co needs to be determined from
relation to the content of Si. For the grain refinement with
purpose of strength improvement required in applications, it is
necessary that the ratio Co/Si in the first and third invention
copper alloys is determined to be higher than 0.005 mass percent
and the ratio Co/Si in the second invention copper alloy is
determined to be higher than 0.02. In other words, when Co/Si dose
not reach these values, there is a little formation of said
precipitate and the effect of grain-growth inhibition are not
shown, and then it is difficult to obtain the strength needed in
applications of said invention copper alloys. Furthermore, in order
to show the growth inhibition effect of crystal grain enough and
improve the strength more, in the first and third invention copper
alloys, it is preferable that Co/Si is higher than 0.01 and more
preferable that Co/Si is high than 0.02 mass percent. In addition,
the preferable and more preferable values in the second invention
copper alloy are higher than 0.04 and 0.06, respectively.
[0049] As described above, in the relation to Si content, Co
content must be determined to satisfy the ratio Co/Si which becomes
higher than the predetermined values, and since said precipitate
becomes rough and increases, the bending characteristics are
obstructed. For example, when Co/Si in the first invention copper
alloy used as the rolled stock becomes higher than 0.5 or Co/Si in
the third invention copper alloy used as the wire drawing material
or the manufactured piece becomes higher than 0.4, the bending
characteristics decreases suddenly. Additionally, even in the
second invention copper alloy whose strength has not to satisfy the
strength condition required in the first invention copper alloy,
when Co/Si exceeds 1.5, it becomes difficult to ensure the minimum
condition required for the bending characteristics. Therefore, the
upper limit of Co/Si must be determined by comparing said point
with the effect of grain growth inhibition, taking the
applications, worked history and shapes into consideration in this
invention copper alloy. Concretely, the range of Co/Si is
determined as follows. In other words, it is necessary that the
upper limit of Co/Si in the first invention copper alloy satisfies
the relationship Co/Si.ltoreq.0.5, and the preferable and optimum
relationships are Co/Si.ltoreq.0.3 and Co/Si.ltoreq.0.2,
respectively. In addition, in the second invention copper alloy, it
is necessary to satisfy the relationship Co/Si.ltoreq.1.5, and the
preferable and optimum relationships are Co/Si.ltoreq.1 and
Co/Si.ltoreq.0.5, respectively. Furthermore, in the third invention
copper alloy, it is necessary to satisfy the relationship
Co/Si.ltoreq.0.4, and the preferable and optimum relationships are
Co/Si.ltoreq.0.2 and Co/Si.ltoreq.0.15, respectively.
[0050] Fe and Ni show the same effect inhibiting crystal grain as
Co (exactly, its effect due to Fe, Ni is less than or equal to the
effect of Co). Therefore, it is possible to contain Fe, Ni as
substitutive element of Co. Of course, further improvement of the
effect can be expected by co-adding Fe and Ni together with Co. In
the case that Fe and/or Ni are added in substitution of Co or with
Co, those additions have the remarkable effect in economy because
of decreasing of the expensive Co. As to the relationship
(Co+Fe+Ni)/Si among the contents of Fe, Ni and Si in the case of
the additions of Fe and/or Ni, the content of Fe or Ni is adjusted
to be equal to the content of Co, and (Co+Fe+Ni)/Si is set to be
equal to the value of Co/Si in single addition of Co, in all of
first, second and third invention copper alloys. This admixture is
based upon the reason described above on the relationship Co/Si
between the contents of Co and Si. In other words, the relationship
(Fe+Ni+Co)/Si in the first invention copper alloy is 0.005 to 0.5
(preferably 0.01 to 0.3, more preferably 0.002 to 0.2), and said
relationship in the second invention copper alloy is 0.02 to 1.5
(preferably 0.04 to 1, more preferably 0.06 to 0.5), and said
relationship in the third invention copper alloy is 0.005 to 0.4
(preferably 0.01 to 0.2, more preferably 0.02 to 0.15).
Incidentally, since Fe and Ni can become substitutive elements with
the same function as Co, the total content in the case that two or
three elements selected from a group of Fe, Ni and Co are added
must be equal to the content of the single addition of Co (the
content of Co described above). However, in the case that two or
three elements selected from Fe, Ni and Co are added, the upper
limit of co-addition content of Fe, Ni and Co (total content) is
permitted to be higher than the Co content by about 0.05 mass
percent under consideration of the solid solution and
precipitation. From said consideration, in the case that two or
three elements selected from Fe, Ni and Co are co-added, it is
desirable for the upper limit of total content (Fe+Ni+Co) to be set
higher than the Co content by 0.05 mass percent. In other words, it
is desirable that this total content (Fe+Ni+Co) in the first and
second invention copper alloys are 0.005 to 0.55 mass percent (more
preferably 0.01 to 0.35 mass percent, much more preferably 0.02 to
0.25 mass percent), and it is desirable that said total content in
the third invention copper alloy is 0.005 to 0.35 mass percent
(preferably 0.01 to 0.25 mass percent, much more preferably 0.02 to
0.2 mass percent).
[0051] Sn shows the strength improvement function, grain refinement
function and improvement function of stress relaxation
characteristic, corrosion resistance and wear resistance, etc. In
the first and third invention copper alloys, in order to show the
strength improvement function, grain refinement function,
improvement function of heat resistance in matrix and improvement
function of stress relaxation characteristic, corrosion resistance
and wear resistance, it is necessary that the Sn content is higher
than 0.03 mass percent, and it is preferable to be higher than 0.05
mass percent. However, when the Sn content becomes higher than 1.5
mass percent or 1 mass percent in the first invention copper alloy
used as the rolled stock or the third invention copper alloy used
as wire drawing material, respectively, the bending characteristics
decrease suddenly. Therefore, in order to ensure the bending
characteristics, it is necessary that the Sn content in the first
and third invention copper alloys is less than 1.5 mass percent and
less than 1 mass percent, respectively. Additionally, in order to
ensure enough the bending characteristics in both the first and
third invention copper alloys, it is preferable for the Sn content
to be less than 0.7 mass percent, and it is optimum to be less than
0.5 mass percent.
[0052] On the other hand, in the second invention copper alloy
which has lower minimum strength than the first and third invention
copper alloys, it is preferable to try the strength improvement,
grain refinement, improvement of stress relaxation characteristic,
stress corrosion crack resistance, corrosion resistance and
improvement of wear resistance, while considering the relation with
Si content. Accordingly, it is necessary for the Sn content to be
higher than 0.2 mass percent, and it is preferable to be higher
than 1 mass percent and more preferable to be higher than 1.2 mass
percent corresponding to required strength. However, when the Sn
content exceeds 3 mass percent, the hot workability is obstructed,
and then the bending characteristics become lower, too. Therefore,
in order to ensure the workability, it is necessary for Sn content
to be less than 3 mass percent, and it is preferable to be less
than 2.6 mass percent so as to ensure more satisfactory
hot-workability and bending characteristics, and more preferable to
be less than 2.5 mass percent.
[0053] Additionally, in the case that Sn is added, it is necessary
that its content is determined by considering the relationship
(Si/Sn) with the Si content. In the first invention copper alloy
whose strength improvement is a principal purpose, when high
strength is obtained with increase of Si content, ductility such as
bending characteristics decreases remarkably for Si/Sn<1.5.
Therefore, in the first invention copper alloy, it is necessary for
the Sn content to satisfy the relationship Si/Sn.gtoreq.1.5.
Furthermore, in order to ensure said ductility enough, it is
preferable to satisfy the relationship Si/Sn.gtoreq.2, and it is
optimum to satisfy the relationship Si/Sn.gtoreq.3. Moreover, in
the third invention copper alloy that Sn content is suppressed to a
little amount slightly comparing with the first invention copper
alloy, from the same reasons described above, it is necessary for
Sn content to satisfy the relationship Si/Sn.gtoreq.1. Furthermore,
in order to ensure said ductility enough, it is preferable for the
Sn content to satisfy the relationship Si/Sn.gtoreq.1.5, and it is
optimum to satisfy the relationship Si/Sn.gtoreq.2.
[0054] On the other hand, in the second invention copper alloy of
which electric conductivity is required so as to balance with the
strength, the addition of Si is restricted. Therefore, in order to
ensure the high strength without loss of the ductility, it is
necessary for Sn content to satisfy the relationship
Si/Sn.ltoreq.0.5 with Si content. For more improvement of the
ductility and strength, the preferable and optimum relationships
are Si/Sn.ltoreq.0.4 and Si/Sn.ltoreq.0.3, respectively.
[0055] At least one element selected from a group of P, Sb, As, Sr,
Mg, Y. Cr, La, Ti, Mn, Zr, In and Hf is added according as the
applications of said alloys, and the effects are mainly the grain
refinement, improvement of hot workability, improvement of
corrosion resistance, action making the accessory elements
mixturing inevitably harmless and improvement of stress relaxation
characteristic, etc. Such effects are hardly expected in the case
that the content of each element is less than 0.003 mass percent,
and on the contrary the effects balanced with the additive quantity
are not obtained in the case beyond 0.3 mass percent. Accordingly,
the addition is useless in economy and rather loses the bending
characteristics. However, in the third invention copper alloy with
much Zn content, P, Sb and As are especially added for the
improvement of dezincification corrosion resistance and stress
corrosion cracking resistance. Similarly to the case described
above, the effects of P, Pb and As added for such purposes scarcely
appear in the addition less than 0.005 mass percent. On the other
hand, when the P content exceeds 0.2 mass percent, adversely the
cold bending characteristics are lost. Therefore, for the additions
of P. Sb and As in the third invention copper alloy, it is
necessary for the contents to be 0.005 to 0.2 mass percent, and in
the case adding at least two kinds of element from P. Sb and As, it
is necessary for the total content to be 0.005 to 0.25 mass
percent.
[0056] By the way, annealing is generally adopted for the heat
treatment to obtain recrystallization materials (recrystallization
treatment), where the annealing keep plastic working blank
mentioned in said (1) the temperature of 200 to 600.degree. C. for
20 minutes to 10 hours. In the heat treatment usually carried out
by batch processing system, when the time of heat treatment is
long, the grains recrystallized at the early stage of heat
treatment gradually grow, and then there is possibility that the
uniform grain refinement is obstructed, even if the effect of grain
growth inhibition appears by the Co addition. However, in the case
with such possibility, when the heat treatment (rapid heating
treatment at high temperature) of molding material is performed in
a short time at higher temperature (body temperature of molding
material) than general annealing temperature, the grain refinement
due to the recrystallization for both Co addition and no addition
is preferably carried out by the growth inhibition of early
recrystallized grains. In other words, the recrystallization in
many nucleation sites is realized by acting the large thermal
energy almost simultaneously in a short time, because the time span
generating the crystal growth is not given. To be concrete, for
example, the crystalline structure of molding material are
completely recrystallized by the heat treatment of said plastic
working blank in the range from 450 to 750.degree. C. for 1 to 1000
seconds.
[0057] In addition, the first, second and third invention copper
alloys are generally produced as the recrystallization materials of
(1), cold working materials of (2) and manufacture pieces of
(3)(4), and alloy characteristics such as strength are improved
more by adding the following treatment in the manufacturing
process.
[0058] For example, in the case that a working rate in the cold
working before obtaining the recrystallized materials is higher
than 30 percent (preferably 60 percent), and more concretely when
the rolling or wire drawing rate of the cold working in the process
obtaining the plastic working blank of (1) is higher than 30
percent (preferably 60 percent), the strength improvement due to
the grain refinement is effectively reached by promoting the
refinement. In other words, in order that the grain refinement can
be caused, the nucleation sites are necessary. As mentioned above,
the nucleation sites increase by the cold working with the higher
working rate, and the increment rate of nucleation sites becomes
large with increasing of working rate. Furthermore, since the
recrystallization originates in releasing of strain energy, more
fine grains are obtained by increasing of shearing strain through
said cold working. As a result, the strength improvement due to the
grain refinement is effectively reached. Incidentally, it is
preferable that the plastic working blank performed the last
recrystallization treatment has the small mean size of grains, and
concretely the mean grain size is less than 20 .mu.m (preferably
less than 10 .mu.m). As the mean crystal grain size before
recrystallization becomes small, the places causing the
recrystallized nucleation in the following heat treatment increase,
and in particular, when dislocation density at the grain boundaries
becomes higher, it is easy to form nucleation sites. However, since
the strength increases with decreasing of the mean grain size, the
energy cost for manufacturing the high strength copper alloy
becomes expensive, and manufacturing time becomes longer.
Therefore, it is preferable that the mean grain size of plastic
working blank in (1) is determined from balance with said working
rate. In addition, when the recrystallization materials lack the
strength, this materials can obtain higher strength by performing
the cold working or cold drawing with the working rate of 10 to 60
percent.
[0059] Furthermore, in the case that said plastic working blank is
obtained, when the rolling or wire drawing work of one path is
performed, it is preferable that the rolling or wire drawing rate
is set to be large (higher than 15 percent, preferably 25 percent).
The more refinement of recrystallized grains can be realized by
increment of the shearing strain and nucleation sites resulting
from the cold working that the rolling and wire drawing rates are
higher. In addition, if the rolling is carried out by using of the
roll of small diameter or extremely large diameter, or if the wire
drawing is carried out by wire dice with large dice angle or
extremely small dice angle, the nucleation sites or the local
distortion energy increases, so that the further refinement of
recrystallized grain can be effectively realized. Furthermore, if
the rolling is carried out by the rolling method with different
peripheral speed, and in other words if the rolling is carried out
varying the velocity by use of the rolling machine providing for
top and bottom rolls having different diameters, the large shearing
strain is given to the rolling material, so that the grain
refinement can be reached.
[0060] Additionally, in each invention copper alloy, according to
those applications, the spring elastic limit and stress relaxation
characteristic can be remarkably improved by performing the
suitable heat treatment (generally annealing in range of 150 to
600.degree. C. for 1 second to 4 hours) without recrystallization.
Concretely, heat treatment is carried out for the cold working
materials of (2) (including cold working materials in (4)) or the
manufacture pieces of (3) (4), for instance, under the condition of
200.degree. C. for 2 hours or 600.degree. C. for 3 seconds.
EXAMPLES
[0061] As embodiment 1, the copper alloy of composition shown in
tables 1 to 4 was dissolved in atmospheric air, and prism-shaped
ingots of 35 mm in thickness, 80 mm in width and 200 mm in length
were obtained. And intermediate plate materials of 6 mm in
thickness were formed by hot rolling (four paths) of this ingot at
850.degree. C., and the materials after acid cleaning became final
plate materials of 1 mm in thickness by the cold rolling. Each
final plate material was performed the heat treatment for one hour
at temperature causing the recystallization of 100 percent (called
"recrystallization temperature"), so that there were obtained the
first invention copper alloy from No.101 to No.186 by performing
complete recrystallization treatment of structure. For the
recrystallization treatment, in advance, samples (a square plate
with one side of about 20 mm) picked up from each final plate
material were annealed for one hour at each temperature rising with
spacing of 50.degree. C. starting from 300.degree. C., and the
lowest temperature causing the complete recrystallization was found
out, so that the lowest temperature was determined as said
recrystallization temperature of the samples (refer to Tables 15 to
17).
[0062] Furthermore, the final plate materials of the same quality
(same form, same composition) as composing materials of alloy
No.102, No.107, No.111, No.154 and No.180 were obtained due to the
same process described above, and these final plate materials were
recrystallization-treated under condition different from said
condition, so that there were obtained the first invention copper
alloy No.102A, No.107A, No.111A, No.154A and No.180A with the same
composition as No.102, No.107, No.111, No.152 and No.175,
respectively. In other words, the first invention copper alloy
No.102A, No.107A, No.111 A, No.154A and No.180A were obtained by
the recrystallization treatment (rapid heating treatment at higher
temperature) in which the heating was maintained for a short time
at much higher temperature than recrystallization temperature,
where the temperature a (.degree. C.) and heating time b (second)
are shown as "a(b)" in the column titled "recrystallization
temperature" in Tables 15 to 17. For example, "480(20)" in column
of "recrystallization temperature" of No.102A in Table 15 means the
heating at 480.degree. C. for 20 seconds.
[0063] As embodiment 2, the copper alloy of composition shown in
Tables 5 to 8 was dissolved in atmospheric air, and prism-shaped
ingots of 35 mm in thickness, 80 mm in width and 200 mm in length
were obtained. And intermediate plate materials of 6 mm in
thickness are formed by hot rolling (four paths) of this ingot at
850.degree. C., and the materials after acid cleaning became final
plate materials of 1 mm in thickness by the cold rolling. Each
final plate material was performed by the heat treatment
(annealing) for one hour at temperature causing the
recystallization of 100 percent (by recrystallized treatment), so
that there were obtained the second invention copper alloy from
No.201 to No.281. In addition, the recrystallization temperature
was determined in advance by method similar to example 1 (refer
Table 18 to 20).
[0064] Furthermore, the final plate materials of the same quality
as composing materials of alloy No.202, No.209, No.250 and No.265
were obtained due to the same process described above, and these
final plate materials were recrystallized by the above-described
rapid heating treatment at higher temperature, so that there were
obtained the second invention copper alloy No.202A, No.209A,
No.250A and No.265A with the same composition as No.202, No.209,
No.250 and No.265, respectively. In other words, condition
obtaining alloy No.202A, No.209A, No.250A and No.265A in the rapid
heating treatment at high temperature (a(.degree. C.) and heating
time b (second)) is described as "a(b)" in column titled
"recrystallization temperature" of Tables 18 to 20 by the same
description as Tables 15 to 17.
[0065] As embodiment 3, the copper alloy of composition shown in
Tables 9 to 12 was dissolved in atmospheric air, and column-shaped
ingots of 95 mm in diameter and 180 mm in length were obtained.
Round bars of 12 mm in diameter were obtained by extruding press
(500 t) while heating the ingots at 780.degree. C. This round bars
after cleaning were worked by wire drawing into 8 mm in diameter,
and after heat-treating the round bars for one hour at 500.degree.
C. and cleaning them, the wires of 4 mm in diameter (molding
materials) were obtained by wire drawing. Furthermore, each wire
was heat-treated (annealing) for 1 hour at the temperature
(recrystallization temperature) that recrystallization of 100
percent was realized (recrytallization treatment), and third
invention copper alloys No.301 to 397 were obtained. For the
recrystallization treatment, in advance, samples (wires of 20 mm in
length (4 mm in diameter)) picked up from each wire were annealed
for one hour at each temperature rising with spacing of 50.degree.
C. starting from 300.degree. C., and the lowest temperature causing
the complete recrystallization was found out, so that the lowest
temperature was determined as said recrystallization temperature of
the samples (refer to Tables 21 to 24).
[0066] Furthermore, the wires (molding materials) of the same
quality as composing materials of alloy No.302, No.314 and No.338
were obtained due to the same process described above, and these
wires were recrystallized by the above-described rapid heating
treatment at higher temperature, so that there were obtained the
third invention copper alloy No.302A, No.314A and No.338A with the
same composition as No.302, No.314 and No.338, respectively. The
condition obtaining alloy No.302A, No.314A and No.338A due to the
rapid heating treatment at high temperature (temperature a
(.degree. C.) and heating time b (second)) is described as "a(b)"
in column titled "recrystallization temperature" of Tables 21 to 24
by the same descriptive method as Tables 15 to 17.
[0067] As comparative example 1, first comparative example alloys
No.401 to No.422 shown in Table 13 were obtained on the basis of
the same process as the first embodiment. In addition, as
comparative example 2, second comparative example alloys No.423 to
No.431 shown in Table 14 were obtained due to the same process as
third embodiment. Incidentally, the first comparative example
alloys No.401 to 407, respectively, have the same compositions as
C2100, C2200, C2300, C2400, C2600, C2680 and C4250 of Japanese
Industrial Standards (JIS), and the second comparative example
alloys No.423 and 424, respectively, have the same compositions as
C2600 and C2700 of JIS. Additionally, in Tables 1 to 12, the
expression of relationship "(Co+Fe+Ni)/Si" for alloy that contains
only Co without Fe and Ni is replaced by "Co/Si".
[0068] Incidentally, since the following problems in manufacturing
process occurred for the comparative example alloys No.421, No.425,
No. 427 and No.431, the manufacturing has been abandoned because of
impossibility of manufacturing thereafter. In other words, No.421
causes large cracking in the step that ingots are hot-rolled, and
No.425 cannot be hot-extruded. No.427 and No.431 rupture in the
wire drawing process. Accordingly, their manufacturing was
abandoned because it is difficult to carry out the process
thereafter.
[0069] In the first invention copper alloys of No.101 to 186 and
No.102A, 107A, 111A, 154A, 180A, the second invention copper alloys
of No.201 to 281 and No.202A, 209A, 250A, 265A, the third invention
copper alloys of No.301 to 397 and No.302A, 314A, No.338A, and the
first and second comparative example alloys of No.401 to 431
(except for No.421, No. 425, No. 427 and No. 431 abandoned the
manufacturing), the mean grain size D (.mu.m) of recrystallized
structures was measured on the basis of intercept method with the
use of optical image (JIS-H0501). The results are shown in Tables
15 to 26.
[0070] In the first invention copper alloys of No.101 to No.186 and
No.102A, 107A, 111A, 154A, 180A, the second invention copper alloys
of No.201 to 281, No.202A, 209A, 250A, 265A and the first
comparative example alloys No. 401 to 422 (except for No.421), the
electric conductivity was measured. The results are shown in Tables
15 to 26 and Table 25. In addition, the electric conductivity (%
IACS) is defined by a percentage of the ratio of the volume
specific resistance of international standard soft copper
(17.241.times.10.sup.-9 .mu..OMEGA..multidot.m) divided by that of
said alloy.
[0071] Additionally, in the first invention copper alloys of No.101
to No.186 and No.102A, 107A, 111A, 154A, 180A, the second invention
copper alloys of No.201 to 281, No.202A, 209A, 250A, 265A and the
first comparative example alloys of No. 401 to 422 (except for
No.421), proof stress (0.2% proof stress), tensile strength and
elongation were measured by tensile test using an Amsler-type
universal testing machine. Furthermore, after each alloy was
cold-rolled until its thickness becomes 0.7 mm, 0.2% proof stress,
tensile strength and elongation of the rolling materials (called
"post workpiece") were measured by the same tensile test as one
described above, and then evaluation of bending characteristics and
stress corrosion cracking test were carried out. The results are
shown in Tables 15 to 20 and Table 26.
[0072] In addition, for the first invention copper alloys of No.101
to No.186 and No.102A, 107A, 111A, 154A, 180A and the second
invention copper alloys of No.201 to 281, No.202A, 209A, 250A,
265A, it goes without saying that the post workpieces obtained by
30% rolling are also high strength copper alloy of the present
invention.
[0073] In addition, the bending characteristics are evaluated from
bending rate R/t at cracked moment (R: inside radius at bending
positions). This cracking is suffered when the samples that are
vertically cut from the worked pieces to the rolling direction are
bend in W shape. In Tables 12 to 17 and Table 22, the pieces that
the cracking is not caused for R/t=0.5 are indicated by a symbol
.circleincircle. as superior bending characteristics. The pieces
that the cracking is not caused for R/t=1.5 but is found for
0.5.ltoreq.R/t<1.5 are indicated by a symbol .smallcircle. as
preferable bending characteristics (there is no problem in
application). The pieces that the cracking is not caused for
R/t=2.5 but is found for 1.5.ltoreq.R/t<2.5 are indicated by a
symbol .DELTA. as general bending characteristics (there is problem
in applications but it is possible to use). The pieces that the
cracking is caused for R/t=2.5 are indicated by a symbol X as
superior bending characteristics (it is difficult for applications
to use).
[0074] In addition, testing of stress corrosion cracking is carried
out by use of test container and testing liquid prescribed in
JISH3250, and characteristics of stress corrosion cracking
resistance are evaluated from the relationship between ammonia
atmosphere exposure time and stress relaxation rate (stress of
proof stress value 80% of the post workpiece is added on the
surface of the post workpiece) by using the fluid which mixed
ammonia fluid and water, where two quantities are equal. In Tables
15 to 20 and Table 25, the pieces that the stress relaxation rate
is less than 20% in the exposure for 75 hours are indicated by a
symbol .circleincircle. as superior bending characteristics. The
pieces that the stress relaxation rate is higher than 20% in the
exposure for 75 hours but less than 20% in the exposure for 30
hours are indicated by a symbol .smallcircle. as superior bending
characteristics (there is no problem in application). The pieces
that the stress relaxation rate is less than 20% in the exposure
for 12 hours are indicated by a symbol .DELTA. as general bending
characteristics (there is problem in applications but it is
possible to use). The pieces that the stress relaxation rate is
higher than 20% in the exposure for 12 hours are indicated by a
symbol X as superior bending characteristics (it is difficult for
applications to use).
[0075] Additionally, in the third invention copper alloys of No.301
to 397 and No.302A, 314A and 338A, the second invention copper
alloys of No.423 to 431 (except No.425, No.427 and No.431 of
abandoned manufacture), tensile strength and elongation are
determined from tensile testing with use of an Amsler-type
universal testing machine.
[0076] Furthermore, each alloy is straightened to 0.7 mm in
thickness, and tensile strength and elongation in the wire drawing
material (called "post workpiece") are determined by the same
tensile testing as being described above. Additionally, evaluation
of bending characteristics and testing of stress corrosion cracking
are carried out. The results are shown in Tables 21 to 24 and Table
26. In addition, the post workpieces are obtained by the wire
drawing of the third invention copper alloys of No.301 to 397 and
No.302A, 314A and 338A and the second invention copper alloys of
No.201 to 281, No.202A, 209A, 250A and 265A, and it go without
saying that the after working pieces are also the high strength
copper alloy of the present invention.
[0077] Additionally, the bending characteristics was evaluated from
bending rate R/d when the post workpieces were bent to 90 degree by
use of V-block, and the cracking was caused (R (mm): radius of
curvature of inner side at the bending portion, d (mm): radius of
post workpices). In Tables 18 to 22, the pieces that the cracking
is not caused for R/d=0 are indicated by a symbol .circleincircle.
as superior bending characteristics. The pieces that the cracking
is not caused for R/d=0.25 but found for 0.ltoreq.R/d<0.25 are
indicated by a symbol .smallcircle. as preferable bending
characteristics (there is no problem in application). The pieces
that the cracking is not caused for R/d=0.5 but found for
0.25.ltoreq.R/d<0.5 are indicated by a symbol .DELTA. as general
bending characteristics (there is problem in applications but it is
possible to use). The pieces that the cracking is caused for
R/d=0.5 are indicated by a symbol X as inferior bending
characteristics (it is difficult to use in applications).
[0078] In addition, the stress corrosion cracking test using the
post workpiece used for the evaluation of bending characteristics
with R/d=1.5 and 90 degree bending is carried out by use of test
device and test liquid prescribed in JISH3250. After ammonia
exposure using the fluid that mixed equal amounts of ammonia
aqueous solution and water, and pickling due to sulfuric acid, the
stress corrosion cracking resistance was evaluated from the
research of cracking existence due to the stereoscopic microscope
with 10 times magnification. In Tables 15 to 20 and Table 25, the
pieces that the cracking is not caused in the exposure for 40 hours
are indicated by a symbol .circleincircle. as superior corrosion
cracking resistance. The pieces that the cracking is caused in the
exposure for 40 hours but is not caused in the exposure for 15
hours are indicated by a symbol .smallcircle. as preferable
corrosion cracking resistance (there is no problem in application).
The pieces that the cracking is caused in the exposure for 15 hours
but is not caused in the exposure for 6 hours are indicated by a
symbol .DELTA. as general corrosion cracking resistance (there is
problem in applications but it is possible to use). The pieces that
the cracking is caused in the exposure for 6 hours are indicated by
a symbol X as inferior stress corrosion cracking resistance (it is
difficult to use in applications).
1 TABLE 1 Alloy Alloy composition (mass %) No. Cu Zn Si Co Fe P Sr
Y Cr La Hf Zn - 2.5Si (Co + Fe + Ni)/Si Embodiment 1 101 remainder
10.0 0.98 7.550 102 remainder 10.3 1.50 6.550 102A remainder 10.3
1.50 6.550 103 remainder 9.6 1.58 0.07 5.650 104 remainder 11.1
1.43 0.05 7.525 105 remainder 10.4 1.51 0.02 6.625 106 remainder
8.5 1.66 0.03 4.350 107 remainder 9.7 2.07 4.525 107A remainder 9.7
2.07 4.525 108 remainder 6.8 2.33 0.975 109 remainder 16.1 0.73
14.275 110 remainder 10.0 1.02 0.11 7.450 0.108 111 remainder 10.2
1.52 0.12 6.400 0.079 111A remainder 10.2 1.52 0.12 6.400 0.079 112
remainder 11.8 1.44 0.08 0.12 8.200 0.056 113 remainder 9.1 1.57
0.11 0.03 5.175 0.070 114 remainder 10.1 2.01 0.11 5.075 0.055 115
remainder 11.5 2.32 0.14 5.700 0.060 116 remainder 11.0 1.52 0.01
7.200 0.005 117 remainder 10.2 1.51 0.06 6.425 0.040 118 remainder
9.3 1.08 0.23 6.600 0.213 119 remainder 4.8 1.58 0.07 0.850 0.044
120 remainder 18.1 1.39 0.15 14.625 0.108 121 remainder 13.6 1.26
0.09 10.450 0.071 122 remainder 10.2 1.49 0.03 6.475 0.020 123
remainder 11.2 0.69 0.07 9.475 0.101 124 remainder 13.2 1.81 0.12
8.675 0.066
[0079]
2 TABLE 2 Alloy composition (mass %) Alloy Zn - (Co + Fe + No. Cu
Zn Si Co Fe Ni Sn As Mg Zr In 2.5Si Ni/Si Si/Sn Embodiment 1 125
remainder 6.6 1.31 0.27 5.325 0.206 126 remainder 10.3 1.95 0.10
0.05 5.425 0.051 127 remainder 9.8 0.88 0.39 7.600 0.443 128
remainder 7.1 1.62 0.06 3.050 0.037 129 remainder 9.5 2.01 0.12
4.475 0.060 130 remainder 10.0 1.63 0.06 0.01 5.925 0.043 131
remainder 9.4 1.04 0.10 0.06 6.800 0.154 132 remainder 10.8 1.58
0.04 0.07 6.850 0.070 133 remainder 9.3 1.66 0.08 0.02 5.150 0.060
134 remainder 7.8 1.81 0.16 0.12 3.275 0.155 135 remainder 12.1
1.73 0.05 0.06 7.775 0.064 136 remainder 11.8 1.12 0.19 0.08 9.000
0.241 137 remainder 9.7 1.48 0.04 0.07 6.000 0.074 138 remainder
8.8 1.63 0.12 0.01 4.725 0.080 139 remainder 8.6 1.69 0.11 0.09
0.07 4.375 0.160 140 remainder 5.3 1.32 0.03 0.01 0.04 2.000 0.058
141 remainder 10.2 0.81 0.01 0.02 0.08 8.175 0.136 142 remainder
9.4 1.64 0.34 5.300 4.824 143 remainder 8.9 1.56 1.01 5.000 1.545
144 remainder 10.6 1.12 0.05 7.800 22.400 145 remainder 8.2 2.41
0.05 0.29 2.175 0.021 8.310 146 remainder 11.3 2.14 0.10 0.42 5.950
0.047 5.095 147 remainder 7.6 0.57 0.12 0.21 6.175 0.211 2.714 148
remainder 10.8 1.74 0.11 0.35 6.450 0.063 4.971 149 remainder 10.6
1.52 0.09 0.29 0.03 6.800 0.059 5.241 150 remainder 9.6 1.63 0.10
0.30 0.01 0.03 5.525 0.061 5.433 151 remainder 9.8 1.67 0.07 0.25
0.02 5.625 0.042 6.680
[0080]
3 TABLE 3 Alloy composition (mass %) (Co + Fe + Alloy Zn - Ni)/ No.
Cu Zn Si Co Fe Ni Sn P Sb Sr Mg Ti Mn Zr Hf 2.5Si Si Si/Sn Em- 152
re- 10.7 1.59 0.11 0.32 0.02 0.01 4.675 0.069 4.969 bodi- mainder
ment 153 re- 5.9 1.84 0.02 0.23 1.300 0.011 8.000 1 mainder 154 re-
8.7 1.76 0.06 0.28 4.300 0.034 6.286 mainder 154A re- 8.7 1.76 0.06
0.28 4.300 0.034 6.286 mainder 155 re- 9.0 1.62 0.47 0.08 4.950
3.447 mainder 156 re- 9.9 1.77 0.09 0.41 0.03 0.05 5.475 0.051
4.317 mainder 157 re- 10.1 1.30 0.44 0.08 6.850 0.338 16.250
mainder 158 re- 9.5 1.61 0.08 0.20 5.475 0.050 8.050 mainder 159
re- 13.3 1.11 0.08 0.21 10.525 0.072 5.286 mainder 160 re- 8.2 1.82
0.12 0.18 3.650 0.066 10.111 mainder 161 re- 4.9 1.79 0.08 0.26
0.425 0.045 6.885 mainder 162 re- 8.9 1.32 0.09 0.82 5.600 0.068
1.610 mainder 163 re- 10.0 2.01 0.12 0.42 4.975 0.060 4.786 mainder
164 re- 11.3 1.38 0.28 0.33 7.850 0.203 4.182 mainder 165 re- 9.0
1.60 0.08 0.25 5.000 0.050 6.400 mainder 166 re- 9.7 1.65 0.06 0.03
0.30 5.575 0.055 5.500 mainder 167 re- 10.5 1.59 0.04 0.07 0.08
6.525 0.069 19.875 mainder 168 re- 11.3 1.45 0.03 0.01 0.12 0.16
7.675 0.028 12.083 mainder 169 re- 8.9 1.62 0.03 0.03 0.18 0.08
4.850 0.037 9.000 mainder 170 re- 9.8 1.58 0.07 0.04 0.11 0.02 0.02
5.850 0.070 14.364 mainder 171 re- 10.0 1.50 0.03 0.05 0.14 0.04
6.250 0.053 10.714 mainder 172 re- 13.2 1.47 0.05 0.05 0.18 9.525
0.068 8.167 mainder 173 re- 7.8 1.24 0.21 0.06 0.12 4.700 0.218
10.333 mainder 174 re- 9.7 1.49 0.09 0.02 0.28 5.975 0.074 5.321
mainder 175 re- 9.5 1.55 0.08 0.01 0.25 0.07 5.625 0.057 6.200
mainder 176 re- 9.3 1.60 0.04 0.04 0.26 0.03 5.300 0.050 6.154
mainder 177 re- 10.2 2.21 0.06 0.05 0.22 4.675 0.050 10.045
mainder
[0081]
4 TABLE 4 Alloy Alloy composition (mass %) No. Cu Zn Si Co Fe Ni Sn
Zn - 2.5Si (Co + Fe + Ni)/Si Si/Sn Embodiment 1 178 remainder 6.9
1.19 0.15 0.14 0.54 3.925 0.244 2.204 179 remainder 8.9 1.68 0.09
0.02 0.09 4.700 0.065 18.667 180 remainder 14.2 1.65 0.03 0.09 0.20
10.075 0.073 8.250 180A remainder 14.2 1.65 0.03 0.09 0.20 10.075
0.073 8.250 181 remainder 9.4 1.62 0.06 0.01 0.02 0.18 5.350 0.056
9.000 182 remainder 10.1 0.89 0.03 0.02 0.01 0.24 7.875 0.067 3.708
183 remainder 11.8 1.45 0.01 0.03 0.02 0.33 8.175 0.041 4.394 184
remainder 8.3 1.20 0.31 0.07 0.05 5.300 0.317 24.000 185 remainder
9.5 1.70 0.15 0.07 5.250 0.129 186 remainder 9.5 1.70 0.10 0.30
5.250 0.059 5.667
[0082]
5 TABLE 5 Alloy Alloy composition (mass %) No. Cu Zn Si Co Fe Ni P
Sr Cr La Mn Zn - 2.5Si (Co + Fe + Ni)/Si Embodiment 2 201 remainder
10.1 0.28 9.400 202 remainder 10.0 0.49 8.775 202A remainder 10.0
0.49 8.775 203 remainder 9.0 0.51 0.21 7.725 204 remainder 10.5
0.45 0.12 9.375 205 remainder 7.7 0.52 6.400 206 remainder 14.0
0.39 13.025 207 remainder 10.2 0.19 0.03 9.725 0.158 208 remainder
9.9 0.31 0.05 9.125 0.161 209 remainder 10.0 0.50 0.12 8.750 0.240
209A remainder 10.0 0.50 0.12 8.750 0.240 210 remainder 9.5 0.52
0.10 0.03 8.200 0.192 211 remainder 8.8 0.50 0.09 0.04 7.550 0.180
212 remainder 10.3 0.46 0.07 0.03 9.150 0.152 213 remainder 9.7
0.33 0.11 8.875 0.333 214 remainder 4.9 0.73 0.21 3.075 0.288 215
remainder 15.8 0.70 0.10 14.050 0.143 216 remainder 8.5 0.43 0.009
7.425 0.021 217 remainder 13.4 0.40 0.05 12.400 0.125 218 remainder
10.5 0.52 0.06 9.200 0.115 219 remainder 8.7 0.47 0.02 7.525 0.043
220 remainder 9.8 0.39 0.07 8.825 0.179 221 remainder 9.8 0.73 0.21
7.975 0.288 222 remainder 8.3 0.44 0.06 7.200 0.136 223 remainder
12.8 0.37 0.07 11.875 0.189 224 remainder 8.1 0.55 0.06 0.03 6.725
0.164 225 remainder 8.9 0.18 0.26 8.450 1.444
[0083]
6 TABLE 6 Alloy composition (mass %) Alloy Zn - (Co + Fe + No. Cu
Zn Si Co Fe Ni Sn Sr Mg Y Ti Zr Hf 2.5Si Ni)/Si Si/Sn Em- 226
remainder 9.2 0.30 0.36 0.02 8.450 1.200 bodiment 2 227 remainder
8.5 0.49 0.45 7.275 0.918 228 remainder 7.8 0.38 0.02 0.06 6.850
0.211 229 remainder 10.1 0.56 0.26 0.05 8.700 0.554 230 remainder
10.8 0.19 0.04 0.02 10.325 0.316 231 remainder 9.7 0.66 0.03 0.06
8.050 0.136 232 remainder 8.8 0.48 0.04 0.04 7.600 0.167 233
remainder 14.8 0.39 0.02 0.03 13.825 0.128 234 remainder 4.8 0.50
0.21 0.02 3.550 0.460 235 remainder 8.5 0.47 0.04 0.05 7.325 0.191
236 remainder 10.0 0.28 0.04 0.02 0.02 9.300 0.286 237 remainder
8.1 0.44 0.03 0.02 0.03 7.000 0.182 238 remainder 10.8 0.57 0.01
0.05 0.02 9.375 0.140 239 remainder 9.7 0.43 1.41 8.625 0.305 240
remainder 8.2 0.18 2.01 7.750 0.090 241 remainder 8.5 0.20 1.99
0.05 8.000 0.101 242 remainder 7.7 0.15 2.06 0.05 0.01 7.325 0.073
243 remainder 9.1 0.23 2.12 0.07 8.525 0.108 244 remainder 12.3
0.51 1.13 11.025 0.451 245 remainder 9.8 0.18 0.38 9.350 0.474 246
remainder 7.9 0.32 0.11 1.75 7.100 0.344 0.183 247 remainder 7.2
0.33 0.09 1.80 0.04 6.375 0.273 0.183 248 remainder 7.5 0.30 0.12
1.77 0.03 6.750 0.400 0.169 249 remainder 7.9 0.29 0.10 1.68 0.03
0.02 7.175 0.345 0.173 250 remainder 9.1 0.28 0.05 1.92 8.400 0.179
0.146 250A remainder 9.1 0.28 0.05 1.92 8.400 0.179 0.146 251
remainder 10.4 0.70 0.12 1.50 8.650 0.171 0.467
[0084]
7 TABLE 7 Alloy Alloy composition (mass %) No. Cu Zn Si Co Fe Ni Sn
Sb As Mg Y In Zn - 2.5Si (Co + Fe + Ni)/Si Si/Sn Embodiment 252
remainder 8.5 0.32 0.18 1.58 7.700 0.563 0.203 7 253 remainder 7.8
0.27 0.15 2.12 0.07 7.125 0.556 0.127 254 remainder 7.4 0.35 0.10
1.75 0.05 6.525 0.286 0.200 255 remainder 8.8 0.21 0.01 1.48 8.275
0.048 0.142 256 remainder 8.4 0.32 0.11 2.28 7.600 0.344 0.140 257
remainder 7.8 0.27 0.09 2.71 7.125 0.333 0.100 258 remainder 10.6
0.14 0.05 0.29 10.250 0.357 0.483 259 remainder 15.1 0.32 0.07 1.56
14.300 0.219 0.205 260 remainder 8.8 0.28 0.08 1.88 8.100 0.286
0.149 261 remainder 9.2 0.23 0.06 1.33 8.625 0.261 0.173 262
remainder 9.0 0.40 0.06 1.75 8.000 0.150 0.229 263 remainder 4.9
0.35 0.08 1.62 4.025 0.229 0.216 264 remainder 8.3 0.74 0.08 1.63
6.450 0.108 0.454 265 remainder 7.7 0.26 0.07 0.02 2.02 7.050 0.346
0.129 265A remainder 7.7 0.26 0.07 0.02 2.02 7.050 0.346 0.129 266
remainder 7.1 0.27 0.06 0.03 2.22 0.06 6.425 0.333 0.122 267
remainder 8.3 0.27 0.08 0.01 2.00 0.02 0.02 7.625 0.322 0.135 268
remainder 6.9 0.44 0.21 0.01 2.18 5.800 0.500 0.202 269 remainder
8.8 0.36 0.02 0.05 1.58 7.900 0.194 0.228 270 remainder 9.3 0.19
0.04 0.02 0.58 8.825 0.316 0.328 271 remainder 7.8 0.32 0.03 0.05
1.49 7.000 0.250 0.215 272 remainder 11.3 0.44 0.03 0.03 1.68
10.200 0.136 0.262 273 remainder 8.7 0.33 0.02 0.05 1.40 7.875
0.212 0.236 274 remainder 10.6 0.22 0.06 0.02 1.90 10.050 0.364
0.116 275 remainder 7.7 0.28 0.03 0.03 1.66 7.000 0.214 0.169 276
remainder 6.8 0.36 0.05 0.02 0.01 1.58 5.900 0.217 0.228 277
remainder 12.5 0.41 0.12 0.05 0.05 2.28 11.475 0.244 0.180
[0085]
8 TABLE 8 Alloy Alloy composition (mass %) No. Cu Zn Si Co Fe Ni Sn
P Sb Zn - 2.5Si (Co + Fe + Ni)/Si Si/Sn Embodiment 2 278 remainder
7.7 0.26 0.01 0.04 0.02 1.77 7.050 0.269 0.147 279 remainder 8.3
0.34 0.09 0.03 1.73 0.05 0.03 7.450 0.353 0.197 280 remainder 9.0
0.35 0.13 2.10 8.125 0.371 0.167 281 remainder 9.0 0.40 0.26 2.00
8.000 0.650 0.200
[0086]
9 TABLE 9 Alloy Alloy composition (mass %) No. Cu Zn Si Co Fe Ni Mg
Ti Mn In Cu - 5Si Zn + 6Si (Co + Fe + Ni)/Si Embodiment 3 301 71.1
27.7 1.22 64.980 35.02 302 70.8 27.8 1.38 63.920 36.08 302A 70.8
27.8 1.38 63.920 36.08 303 71.1 27.5 1.36 0.07 64.270 35.66 304
71.5 27.0 1.41 0.12 64.420 35.46 305 72.6 25.9 1.55 64.800 35.20
306 68.2 31.1 0.68 0.02 64.800 35.18 0.029 307 71.0 28.0 0.97 0.07
66.110 33.82 0.072 308 70.5 28.1 1.33 0.05 63.870 36.08 0.038 309
72.1 26.3 1.38 0.23 65.190 34.58 0.167 310 73.2 25.1 1.61 0.11
65.130 34.76 0.068 311 71.5 26.7 1.72 0.13 62.850 37.02 0.076 312
75.2 22.9 1.77 0.09 66.390 33.52 0.051 313 71.7 26.8 1.43 0.07
64.550 35.38 0.049 314 72.9 25.5 1.56 0.08 65.060 34.86 0.051 314A
72.9 25.5 1.56 0.08 65.060 34.86 0.051 315 72.4 26.0 1.51 0.07 0.05
64.820 35.06 0.046 316 73.1 25.2 1.58 0.07 0.02 0.02 65.210 34.68
0.044 317 71.6 26.9 1.40 0.08 64.620 35.30 0.057 318 72.6 25.7 1.51
0.22 65.020 34.76 0.146 319 68.4 31.0 0.62 0.01 65.272 34.72 0.013
320 72.4 26.1 1.48 0.05 64.970 34.98 0.034 321 67.8 31.5 0.67 0.01
64.471 35.52 0.013 322 75.3 22.7 1.91 0.08 65.760 34.16 0.042 323
71.2 27.3 1.41 0.03 0.05 64.160 35.76 0.057 324 72.3 26.0 1.64 0.01
0.06 64.093 35.84 0.041 325 68.4 30.8 0.65 0.18 0.01 65.110 34.70
0.292
[0087]
10 TABLE 10 Alloy composition (mass %) Alloy Cu - Zn + (Co + Fe +
No. Cu Zn Si Co Fe Ni Sn Sr Y Le Zr In Hf 5Si 6Si Ni)/Si Si/Sn
Embodi- 326 72.5 25.9 1.53 0.05 0.02 64.85 35.08 0.046 ment 3 327
70.6 28.1 1.25 0.06 0.01 64.33 35.60 0.056 328 71.5 27.0 1.44 0.02
0.05 64.29 35.64 0.049 329 71.7 26.8 1.45 0.06 0.03 64.41 35.50
0.062 330 70.7 27.6 1.58 0.04 0.04 62.84 37.08 0.051 331 71.9 26.5
1.55 0.04 0.03 0.03 64.10 35.80 0.045 332 72.2 26.2 1.48 0.03 0.03
0.02 64.84 35.08 0.054 333 71.2 27.3 1.38 0.03 0.05 0.01 0.03 64.30
35.58 0.065 334 71.4 27.0 1.55 0.07 0.01 0.02 63.60 36.30 0.065 335
73.7 24.5 1.61 0.22 65.62 34.16 7.318 336 74.0 23.8 1.52 0.73 66.35
32.92 2.082 337 71.7 26.6 1.42 0.09 64.62 35.12 15.778 338 73.2
25.0 1.59 0.06 0.13 65.27 34.54 0.038 12.231 338A 73.2 25.0 1.59
0.06 0.13 65.27 34.54 0.038 12.231 339 73.0 25.2 1.60 0.05 0.10
0.03 65.02 34.80 0.031 16.000 340 72.8 25.5 1.57 0.05 0.08 0.01
0.03 64.91 34.92 0.032 19.625 341 72.9 25.3 1.59 0.07 0.13 0.04
64.92 34.84 0.044 12.231 342 75.1 22.8 1.82 0.09 0.23 65.96 33.72
0.049 7.913 343 71.5 26.9 1.41 0.15 0.04 64.45 35.36 0.106 35.250
344 72.3 26.0 1.24 0.07 0.37 66.12 33.44 0.056 3.351 345 71.7 26.3
1.19 0.08 0.74 65.74 33.44 0.067 1.608 346 71.9 26.3 1.45 0.21 0.15
64.64 35.00 0.145 9.667 347 72.5 25.6 1.67 0.05 0.20 64.13 35.62
0.030 8.350 348 71.2 27.1 1.55 0.02 0.11 63.47 36.40 0.013 14.091
349 73.7 24.4 1.71 0.07 0.06 0.03 65.18 34.66 0.041 28.500 350 71.8
26.6 1.42 0.06 0.16 64.66 35.12 0.042 8.875 351 75.1 22.7 1.91 0.13
0.05 0.09 65.57 34.16 0.094 21.222
[0088]
11 TABLE 11 Alloy composition (mass %) Alloy Cu - Zn + (Co + No. Cu
Zn Si Co Fe Ni Sn P Sr Mg Y Zr Hf 5Si 6Si Fe + Ni)/Si Si/Sn Em- 352
71.7 26.6 1.45 0.04 0.05 0.21 64.400 35.30 0.062 6.905 bod- 353
73.3 24.9 1.60 0.02 0.07 0.14 65.270 34.50 0.056 11.429 iment 3 354
72.8 25.3 1.58 0.03 0.07 0.18 0.02 64.920 34.78 0.063 8.778 355
73.3 24.8 1.63 0.04 0.05 0.12 0.02 0.02 65.170 34.58 0.055 13.583
356 73.1 25.1 1.61 0.04 0.06 0.09 0.03 0.01 65.013 34.76 0.062
17.889 357 75.6 21.9 1.88 0.07 0.01 0.59 66.152 33.18 0.041 3.186
358 72.1 26.2 1.44 0.05 0.04 0.14 64.930 34.84 0.063 10.286 359
72.7 25.5 1.63 0.02 0.05 0.12 64.530 35.28 0.043 13.583 360 71.4
26.8 1.38 0.18 0.04 0.22 64.480 35.08 0.159 6.273 361 72.8 25.2
1.70 0.06 0.03 0.19 64.320 35.40 0.053 8.947 362 73.8 23.8 1.44
0.03 0.06 0.92 66.550 32.44 0.063 1.565 363 71.9 26.4 1.41 0.02
0.02 0.05 0.21 64.840 34.86 0.064 6.714 364 70.0 28.6 0.75 0.12
0.63 66.250 33.10 0.160 1.190 365 71.0 27.1 1.06 0.06 0.02 0.82
65.700 33.46 0.075 1.293 366 73.1 24.9 1.68 0.02 0.07 0.01 0.18
64.740 34.98 0.060 9.333 367 66.8 32.3 0.63 0.12 0.04 0.02 0.05
63.690 36.08 0.286 12.600 368 72.3 26.3 1.40 0.03 65.270 34.70 369
73.1 25.1 1.65 0.14 64.860 35.00 370 71.7 26.8 1.43 0.06 0.01
64.552 35.38 0.042 371 73.1 25.0 1.72 0.09 0.12 64.470 35.32 0.052
372 72.2 26.2 1.50 0.07 0.05 64.680 35.20 0.047 373 71.9 26.3 1.61
0.13 0.07 63.840 35.96 0.081 374 72.3 26.1 1.47 0.07 0.08 64.930
34.92 0.048 375 71.1 27.5 1.22 0.07 0.02 0.06 65.030 34.82 0.074
376 72.4 25.9 1.53 0.06 0.01 0.09 64.763 35.08 0.044 377 73.0 25.2
1.66 0.05 0.03 0.03 64.730 35.16 0.048 378 73.5 24.7 1.68 0.05 0.03
0.01 0.04 65.090 34.78 0.054
[0089]
12 TABLE 12 Alloy Alloy composition (mass %) No. Cu Zn Si Co Fe Ni
Sn P Sb As Cu - 5Si Zn + 6Si (Co + Fe + Ni)/Si Si/Sn Em- 379 71.6
26.5 1.55 0.28 0.06 63.860 35.80 5.536 bod- 380 72.5 25.4 1.23 0.07
0.81 0.04 66.300 32.78 0.057 1.519 iment 381 72.6 25.5 1.60 0.08
0.15 0.06 64.610 35.10 0.050 10.67 3 382 71.6 26.7 1.54 0.05 0.08
0.08 63.850 35.94 0.032 19.25 383 73.3 24.9 1.60 0.02 0.07 0.14
65.270 34.50 0.056 11.43 384 74.7 23.2 1.72 0.01 0.14 0.22 0.06
68.052 33.52 0.086 7.818 385 73.1 25.1 1.44 0.06 0.01 0.17 0.08
65.943 33.74 0.047 8.471 386 72.6 25.6 1.58 0.03 0.06 0.11 0.06
64.660 35.08 0.057 14.36 387 71.8 26.4 1.46 0.09 0.01 0.03 0.19
0.05 64.472 35.16 0.088 7.684 388 72.5 25.9 1.55 0.04 64.750 35.20
389 73.6 24.6 1.70 0.07 65.100 34.80 390 71.2 27.4 1.26 0.07 0.10
64.900 34.96 0.056 391 73.1 25.1 1.68 0.11 0.03 64.700 35.18 0.065
392 72.1 26.2 1.55 0.07 0.06 0.02 64.350 35.50 0.045 393 72.2 25.8
1.60 0.35 0.05 64.200 35.40 4.571 394 71.0 27.0 1.26 0.06 0.65 0.08
64.700 34.56 0.048 1.938 395 72.0 26.2 1.25 0.08 0.37 0.05 0.06
65.750 33.70 0.064 3.378 396 72.5 25.1 1.53 0.06 0.02 0.72 0.07
0.01 64.850 34.28 0.052 2.125 397 71.5 26.7 1.48 0.04 0.04 0.21
0.03 0.02 0.02 64.100 35.58 0.054 7.048
[0090]
13 TABLE 13 Alloy Alloy composition (mass %) No. Cu Zn Si Co Fe Ni
Sn P Zn - 2.5Si (Co + Fe + Ni)/Si Si/Sn Comparative 401 94.70 5.3
5.30 example 1 402 89.80 10.2 10.20 403 85.10 14.9 14.90 404 79.40
20.6 20.60 405 69.90 30.1 30.10 406 65.20 34.8 34.80 407 88.32 9.5
2.10 0.08 9.50 408 82.08 17.6 0.32 16.80 409 96.47 2.1 1.18 0.25
-0.85 4.720 410 78.36 19.9 1.44 0.09 0.21 16.30 0.063 6.857 411
79.78 17.9 0.52 0.05 1.75 16.60 0.096 0.297 412 96.69 2.8 0.48 0.03
1.60 0.063 413 91.35 8.6 0.04 0.01 8.50 0.250 414 86.41 10.9 2.61
0.08 4.38 0.031 415 87.88 10.4 1.13 0.59 7.58 0.522 416 87.05 11.1
1.23 0.62 8.03 0.504 417 88.43 10.3 0.72 0.55 8.50 0.764 418 88.20
9.8 1.31 0.17 0.26 0.26 6.53 0.527 419 86.90 10.2 1.53 0.09 1.28
6.38 0.059 1.195 420 88.51 9.4 0.76 1.33 7.50 0.571 421 85.97 9.8
0.66 0.07 3.50 8.15 0.106 0.189 422 88.30 8.8 0.45 0.42 0.28 1.75
7.68 1.556 0.257
[0091]
14 TABLE 14 Alloy Alloy composition (mass %) No. Cu Zn Si Co Sn Cu
- 5Si Zn + 6Si (Co + Fe + Ni)/Si Si/Sn Comparative 423 69.80 30.2
69.80 30.20 example 2 424 64.90 35.1 64.90 35.10 425 74.97 23.8
1.23 68.82 31.18 426 66.81 31.9 1.25 0.04 60.56 39.40 0.032 427
74.74 23.0 2.21 0.05 63.69 36.26 0.023 428 65.85 32.8 1.25 0.10
59.60 40.30 0.080 429 67.12 32.5 0.35 0.03 65.37 34.60 0.086 430
68.80 29.3 0.92 0.05 0.95 64.20 34.82 0.054 0.968 431 73.31 23.7
1.80 0.04 1.15 64.31 34.50 0.022 1.565
[0092]
15 TABLE 15 Mechanical properies Mean Recrystal- Mechanical
properies (Post workpiece) Bending grain lization Proof Tensile
Proof Tesile characteristics Corrosion Electro- Alloy size
temperature stress strength Elongation stress strength Elongation
(Post cracking conductivity No. (.mu.m) (.degree. C.) (N/mm.sup.2)
(N/mm.sup.2) (%) (N/mm.sup.2) (N/mm.sup.2) (%) workpiece)
resistance (% IACS) Em- 101 2.4 350 308 416 45 504 572 15
.circleincircle. .largecircle. 16 bod- 102 2.2 350 312 481 44 575
676 11 .largecircle. .largecircle. 12 iment 102A 1.8 480(20) 367
493 45 602 691 12 .largecircle. .largecircle. 12 1 103 2.0 400 347
493 45 593 688 11 .largecircle. .largecircle. 12 104 2.0 400 339
491 44 592 685 11 .largecircle. .largecircle. 12 105 2.1 350 328
489 44 586 682 13 .circleincircle. .largecircle. 12 106 2.1 350 331
488 45 584 683 12 .largecircle. .largecircle. 12 107 1.9 350 360
528 43 610 739 7 .DELTA. .circleincircle. 10 107A 1.7 550(10) 403
542 44 627 751 8 .largecircle. .circleincircle. 10 108 2.0 350 355
508 42 599 725 8 .DELTA. .circleincircle. 10 109 2.2 350 309 432 43
513 601 9 .largecircle. .DELTA. 17 110 2.1 400 353 448 41 528 625
14 .circleincircle. .largecircle. 16 111 1.7 400 404 509 40 608 709
12 .circleincircle. .circleincircle. 13 111A 1.5 560(13) 444 525 40
626 723 13 .circleincircle. .circleincircle. 13 112 1.5 400 431 522
42 626 724 13 .circleincircle. .circleincircle. 13 113 1.6 400 417
515 40 615 716 13 .circleincircle. .circleincircle. 13 114 1.6 400
438 558 37 657 780 8 .DELTA. .circleincircle. 11 115 1.1 400 500
610 35 713 834 7 .DELTA. .circleincircle. 10 116 2.1 350 333 496 44
593 691 10 .largecircle. .largecircle. 13 117 1.7 400 372 501 41
622 733 10 .largecircle. .circleincircle. 13 118 1.3 400 399 502 39
591 692 10 .largecircle. .circleincircle. 17 119 2.3 400 312 452 40
548 638 9 .largecircle. .circleincircle. 13 120 1.5 400 475 583 40
640 785 8 .DELTA. .DELTA. 13 121 1.8 400 406 509 43 602 701 11
.largecircle. .largecircle. 14 122 2.0 350 354 493 45 615 705 11
.largecircle. .largecircle. 13 123 2.2 400 310 415 43 501 598 14
.circleincircle. .largecircle. 19 124 1.6 400 439 562 38 543 754 8
.DELTA. .largecircle. 11 125 1.5 450 395 507 34 613 701 9 .DELTA.
.circleincircle. 16 126 1.6 400 429 548 37 648 771 8 .DELTA.
.circleincircle. 11 127 1.4 450 381 456 36 558 639 8 .DELTA.
.largecircle. 19 128 1.9 400 337 470 39 552 657 10 .largecircle.
.circleincircle. 13
[0093]
16 TABLE 16 Mechanical properies Mean Recrystal- Mechanical
properies (Post workpiece) Bending grain lization Proof Tensile
Proof Tesile characteristics Corrosion Electro- Alloy size
temperature stress strength Elongation stress strength Elongation
(Post cracking conductivity No. (.mu.m) (.degree. C.) (N/mm.sup.2)
(N/mm.sup.2) (%) (N/mm.sup.2) (N/mm.sup.2) (%) workpiece)
resistance (% IACS) Em- 129 1.5 400 412 544 38 630 742 9 .DELTA.
.circleincircle. 11 bod- 130 1.5 400 392 512 44 614 725 12
.circleincircle. .circleincircle. 13 iment 131 1.7 400 357 478 40
575 665 12 .circleincircle. .largecircle. 15 1 132 1.3 400 413 517
40 628 730 11 .circleincircle. .circleincircle. 12 133 1.3 400 404
513 40 624 735 11 .circleincircle. .circleincircle. 12 134 1.4 450
430 558 36 559 784 9 .DELTA. .circleincircle. 12 135 1.2 400 430
558 40 561 759 9 .largecircle. .largecircle. 12 136 1.8 400 383 510
37 604 702 9 .DELTA. .largecircle. 16 137 1.4 400 391 507 39 618
713 9 .largecircle. .circleincircle. 13 138 1.3 400 400 515 42 600
708 12 .circleincircle. .circleincircle. 12 139 1.2 450 444 559 36
673 779 7 .DELTA. .circleincircle. 13 140 2.0 400 314 434 40 510
614 14 .circleincircle. .circleincircle. 14 141 1.8 400 321 436 43
522 616 15 .circleincircle. .circleincircle. 18 142 1.9 350 357 499
44 547 689 12 .largecircle. .circleincircle. 12 143 1.7 350 389 512
40 588 702 9 .DELTA. .circleincircle. 11 144 2.3 350 325 447 43 515
627 13 .circleincircle. .largecircle. 16 145 1.3 400 465 585 38 700
810 6 .DELTA. .circleincircle. 10 146 1.1 400 490 606 37 712 822 7
.DELTA. .circleincircle. 11 147 2.3 400 303 403 42 522 580 14
.circleincircle. .largecircle. 18 148 1.2 400 443 565 40 701 787 10
.largecircle. .circleincircle. 12 149 1.3 400 411 536 42 670 757 11
.circleincircle. .circleincircle. 12 150 1.3 400 414 541 43 675 753
11 .circleincircle. .circleincircle. 12 151 1.3 400 410 537 42 677
760 12 .circleincircle. .circleincircle. 12 152 1.2 400 425 552 43
688 770 11 .circleincircle. .circleincircle. 12 153 2.2 400 360 480
40 540 655 12 .largecircle. .circleincircle. 11 154 1.4 400 402 538
41 645 750 11 .largecircle. .circleincircle. 11 154A 1.3 710(5) 426
553 43 658 762 12 .largecircle. .circleincircle. 11 155 1.8 350 363
506 42 593 691 11 .largecircle. .circleincircle. 12 156 1.3 400 449
573 39 708 795 10 .largecircle. .circleincircle. 12 157 1.1 450 434
561 36 706 780 7 .DELTA. .largecircle. 17 158 1.4 400 400 530 40
627 735 11 .circleincircle. .circleincircle. 12
[0094]
17 TABLE 17 Mechanical properies Mean Recrystal- Mechanical
properies (Post workpiece) Bending grain lization Proof Tensile
Proof Tesile characteristics Corrosion Electro- Alloy size
temperature stress strength Elongation stress strength Elongation
(Post cracking conductivity No. (.mu.m) (.degree. C.) (N/mm.sup.2)
(N/mm.sup.2) (%) (N/mm.sup.2) (N/mm.sup.2) (%) workpiece)
resistance (% IACS) Em- 159 1.9 400 392 504 42 592 688 12
.largecircle. .largecircle. 14 bod- 160 1.3 400 412 542 40 623 741
10 .largecircle. .circleincircle. 11 iment 161 2.0 400 355 482 40
560 665 12 .largecircle. .circleincircle. 11 1 162 1.4 400 404 502
39 600 701 8 .DELTA. .circleincircle. 12 163 1.2 400 472 595 36 688
800 7 .DELTA. .circleincircle. 10 164 1.5 450 428 510 34 588 698 9
.DELTA. .largecircle. 14 165 1.6 400 382 510 40 601 705 11
.circleincircle. .circleincircle. 12 166 1.2 400 417 544 40 674 769
10 .largecircle. .circleincircle. 12 167 1.4 400 409 537 41 648 750
11 .circleincircle. .largecircle. 13 168 1.3 400 409 524 40 644 738
11 .circleincircle. .largecircle. 13 169 1.3 400 408 525 40 645 745
11 .circleincircle. .circleincircle. 13 170 1.4 400 410 521 42 646
740 12 .circleincircle. .circleincircle. 13 171 1.4 400 400 517 42
640 730 13 .circleincircle. .circleincircle. 13 172 1.3 400 428 549
40 653 763 10 .largecircle. .largecircle. 13 173 1.9 400 382 474 34
535 654 9 .largecircle. .circleincircle. 14 174 1.4 400 405 519 40
615 719 12 .circleincircle. .circleincircle. 12 175 1.3 400 419 530
41 630 730 13 .circleincircle. .circleincircle. 12 176 1.3 400 420
527 41 628 733 13 .circleincircle. .circleincircle. 12 177 1.1 400
476 599 36 716 823 7 .DELTA. .circleincircle. 10 178 2.0 450 393
487 34 562 673 9 .DELTA. .circleincircle. 14 179 1.5 400 403 520 41
613 720 12 .circleincircle. .circleincircle. 12 180 1.2 400 459 586
38 704 802 8 .DELTA. .largecircle. 11 180A 1.1 630(B) 482 597 38
721 813 9 .largecircle. .largecircle. 11 181 1.3 400 405 519 42 609
714 12 .circleincircle. .circleincircle. 12 182 2.1 400 336 441 43
515 621 13 .circleincircle. .largecircle. 18 183 1.5 400 407 518 42
607 708 10 .largecircle. .largecircle. 13 184 1.4 450 423 491 35
563 662 8 .DELTA. .circleincircle. 16 185 1.2 150 456 571 40 694
784 12 .largecircle. .circleincircle. 12 186 1.2 400 444 567 41 692
778 11 .circleincircle. .circleincircle. 13
[0095]
18 TABLE 18 Mechanical properies Mean Recrystal- Mechanical
properies (Post workpiece) Bending grain lization Proof Tensile
Proof Tesile characteristics Corrosion Electro- Alloy size
temperature stress strength Elongation stress strength Elongation
(Post cracking conductivity No. (.mu.m) (.degree. C.) (N/mm.sup.2)
(N/mm.sup.2) (%) (N/mm.sup.2) (N/mm.sup.2) (%) workpiece)
resistance (% IACS) Em- 201 3.2 350 251 347 41 412 466 15
.circleincircle. .largecircle. 28 bod 202 2.6 350 257 366 41 433
498 14 .circleincircle. .largecircle. 23 iment 202A 2.3 530(15) 287
379 42 451 507 15 .circleincircle. .largecircle. 23 2 203 2.4 400
288 399 41 452 530 14 .circleincircle. .largecircle. 24 204 2.4 400
275 390 41 449 525 14 .circleincircle. .largecircle. 24 205 2.8 350
258 349 41 437 489 13 .circleincircle. .largecircle. 24 206 3.1 350
265 390 42 486 536 11 .largecircle. .DELTA. 25 207 3.1 400 254 346
43 420 484 12 .circleincircle. .largecircle. 33 208 2.8 400 263 372
41 485 542 10 .circleincircle. .largecircle. 29 209 2.3 450 301 412
38 500 565 12 .circleincircle. .largecircle. 27 209A 2.1 520(100)
322 423 40 515 570 13 .circleincircle. .largecircle. 27 210 2.2 450
315 425 40 515 573 13 .circleincircle. .largecircle. 27 211 2.3 450
305 418 41 503 568 14 .circleincircle. .largecircle. 28 212 2.2 450
312 420 40 510 570 13 .circleincircle. .largecircle. 27 213 2.8 450
274 393 37 480 535 10 .circleincircle. .largecircle. 29 214 2.4 450
272 412 34 474 537 9 .largecircle. .circleincircle. 20 215 2.1 400
359 469 42 550 647 8 .largecircle. .DELTA. 20 216 2.4 350 261 362
41 455 510 14 .circleincircle. .largecircle. 24 217 2.5 400 306 411
42 488 558 12 .largecircle. .DELTA. 26 218 2.5 400 277 394 40 476
533 12 .circleincircle. .largecircle. 24 219 2.7 400 257 360 41 448
502 13 .circleincircle. .largecircle. 25 220 2.6 400 259 375 42 469
522 14 .circleincircle. .largecircle. 26 221 2.0 450 322 439 35 513
564 9 .DELTA. .largecircle. 20 222 3.0 400 256 363 42 457 505 13
.circleincircle. .largecircle. 25 223 2.8 400 283 398 41 478 534 12
.circleincircle. .DELTA. 26 224 2.4 400 262 391 40 480 531 12
.circleincircle. .largecircle. 23 225 2.8 400 270 358 42 430 492 12
.circleincircle. .largecircle. 32 226 2.4 450 298 405 37 491 570 9
.DELTA. .largecircle. 28 227 2.1 450 320 438 35 515 592 9 .DELTA.
.largecircle. 27
[0096]
19 TABLE 19 Mechanical properies Mean Recrystal- Mechanical
properies (Post workpiece) Bending grain lization Proof Tensile
Proof Tesile characteristics Corrosion Electro- Alloy size
temperature stress strength Elongation stress strength Elongation
(Post cracking conductivity No. (.mu.m) (.degree. C.) (N/mm.sup.2)
(N/mm.sup.2) (%) (N/mm.sup.2) (N/mm.sup.2) (%) workpiece)
resistance (% IACS) Em- 228 2.7 400 259 356 40 445 488 11
.circleincircle. .circleincircle. 27 bod- 229 2.1 450 333 448 42
543 579 10 .circleincircle. .largecircle. 22 iment 230 2.9 400 259
362 43 449 495 14 .circleincircle. .largecircle. 34 2 231 2.2 400
301 419 42 512 578 13 .circleincircle. .largecircle. 21 232 2.4 400
260 388 42 460 526 13 .circleincircle. .largecircle. 25 233 2.8 400
312 422 43 515 581 11 .largecircle. .DELTA. 25 234 2.3 450 260 377
34 456 499 8 .largecircle. .circleincircle. 21 235 2.4 400 257 386
40 477 525 13 .circleincircle. .largecircle. 25 236 2.8 400 255 375
42 474 510 13 .circleincircle. .largecircle. 30 237 2.4 400 268 376
40 474 514 13 .circleincircle. .largecircle. 25 238 2.3 400 304 408
41 499 553 14 .circleincircle. .largecircle. 23 239 2.6 350 331 410
41 523 590 12 .largecircle. .largecircle. 20 240 3.1 400 313 392 40
530 585 11 .largecircle. .largecircle. 24 241 3.0 400 327 400 41
540 591 12 .largecircle. .largecircle. 24 242 2.8 400 335 399 41
543 590 12 .circleincircle. .largecircle. 24 243 2.8 400 351 415 40
551 600 11 .circleincircle. .largecircle. 24 244 2.7 350 337 433 43
545 612 11 .largecircle. .largecircle. 20 245 3.3 350 256 345 42
425 475 14 .circleincircle. .largecircle. 28 246 1.8 400 354 435 42
600 640 13 .circleincircle. .circleincircle. 22 247 1.7 400 380 443
41 608 655 12 .largecircle. .circleincircle. 22 248 1.8 400 371 438
42 600 645 13 .largecircle. .circleincircle. 22 249 1.8 400 365 435
42 599 642 13 .circleincircle. .circleincircle. 22 250 1.8 400 376
443 43 588 645 11 .circleincircle. .largecircle. 22 250A 1.7
520(20) 390 455 43 600 653 12 .circleincircle. .largecircle. 22 251
1.4 400 396 473 38 617 673 9 .DELTA. .largecircle. 19 252 1.7 400
365 440 40 606 643 11 .circleincircle. .largecircle. 24 253 1.7 450
390 458 38 595 663 10 .largecircle. .circleincircle. 23 254 1.8 400
365 430 40 590 636 11 .circleincircle. .circleincircle. 22
[0097]
20 TABLE 20 Mechanical properies Mean Recrystal- Mechanical
properies (Post workpiece) Bending grain lization Proof Tensile
Proof Tesile characteristics Corrosion Electro- Alloy size
temperature stress strength Elongation stress strength Elongation
(Post cracking conductivity No. (.mu.m) (.degree. C.) (N/mm.sup.2)
(N/mm.sup.2) (%) (N/mm.sup.2) (N/mm.sup.2) (%) workpiece)
resistance (% IACS) Em- 255 2.3 350 302 385 41 470 525 14
.circleincircle. .largecircle. 23 bod- 256 1.7 400 396 469 41 608
679 12 .circleincircle. .largecircle. 21 iment 257 1.8 400 411 472
37 630 693 10 .DELTA. .largecircle. 20 2 258 3.2 400 269 374 43 484
518 11 .circleincircle. .largecircle. 32 259 2.1 400 411 487 42 628
701 8 .DELTA. .DELTA. 21 260 2.0 400 354 434 42 578 625 12
.largecircle. .largecircle. 22 261 2.2 400 323 404 41 530 578 12
.circleincircle. .largecircle. 23 262 2.0 400 355 439 40 575 632 11
.largecircle. .largecircle. 20 263 2.4 450 302 381 40 480 524 12
.circleincircle. .circleincircle. 21 264 1.5 400 366 469 42 619 678
9 .DELTA. .circleincircle. 18 265 1.8 400 363 440 40 566 639 12
.circleincircle. .largecircle. 21 265A 1.7 750(4) 377 450 41 575
645 12 .circleincircle. .largecircle. 21 266 1.7 400 380 448 40 585
650 12 .largecircle. .circleincircle. 20 267 1.7 400 379 452 41 590
665 13 .circleincircle. .largecircle. 21 268 1.4 450 403 492 40 638
700 11 .largecircle. .circleincircle. 20 269 1.8 400 360 438 41 587
624 12 .circleincircle. .largecircle. 21 270 3.0 400 271 371 42 492
530 14 .circleincircle. .largecircle. 28 271 2.0 400 332 413 41 548
590 13 .circleincircle. .largecircle. 23 272 1.7 400 389 465 42 612
664 12 .largecircle. .largecircle. 20 273 1.9 400 334 416 40 555
590 13 .circleincircle. .largecircle. 23 274 2.1 400 388 457 40 574
633 12 .circleincircle. .largecircle. 25 275 2.0 400 334 409 41 536
584 12 .circleincircle. .largecircle. 23 276 1.8 400 332 410 40 537
586 11 .circleincircle. .circleincircle. 22 277 1.5 400 458 531 39
672 721 9 .largecircle. .largecircle. 20 278 2.0 400 341 414 42 550
591 13 .circleincircle. .circleincircle. 23 279 1.7 400 388 460 40
605 658 11 .largecircle. .circleincircle. 22 280 1.7 400 396 475 39
615 680 12 .circleincircle. .circleincircle. 21 281 1.3 450 430 492
35 638 702 9 .largecircle. .circleincircle. 23
[0098]
21 TABLE 21 Mechanical properies Mean Recrystal- Mechanical
properies (Post workpiece) Bending grain lization Proof Tensile
Elonga- Proof Tesile Elonga- characteristics Corrosion Electro-
Alloy size temperature stress strength tion stress strength tion
(Post cracking conductivity No. (.mu.m) (.degree. C.) (N/mm.sup.2)
(N/mm.sup.2) (%) (N/mm.sup.2) (N/mm.sup.2) (%) workpiece)
resistance (% IACS) 301 3.1 300 310 502 38 635 729 6 .largecircle.
.DELTA. 13 302 3.2 300 324 518 35 658 756 6 .largecircle. .DELTA.
13 302A 3.0 500(15) 339 527 37 670 765 7 .largecircle. .DELTA. 13
303 2.9 350 345 533 35 673 788 6 .largecircle. .DELTA. 13 304 2.8
350 352 540 35 685 775 6 .largecircle. .DELTA. 13 305 2.9 300 340
535 36 685 776 6 .largecircle. .largecircle. 12 306 3.3 350 266 453
39 589 667 7 .largecircle. .DELTA. 16 307 2.9 350 305 495 36 621
717 6 .largecircle. .DELTA. 15 308 2.7 350 332 526 34 670 762 6
.largecircle. .DELTA. 13 309 2.2 350 360 541 32 677 774 5 .DELTA.
.largecircle. 14 310 2.4 350 372 569 35 713 824 6 .largecircle.
.largecircle. 12 311 2.3 350 382 580 32 729 841 5 .DELTA.
.largecircle. 12 312 1.9 350 392 580 34 751 860 5 .DELTA.
.largecircle. 11 313 2.6 350 346 541 35 682 784 6 .largecircle.
.largecircle. 13 314 2.4 350 360 556 35 716 811 6 .largecircle.
.largecircle. 12 314A 2.3 550(10) 372 565 36 725 817 7
.largecircle. .largecircle. 12 315 2.3 350 375 567 36 728 819 6
.largecircle. .largecircle. 12 316 2.3 350 376 569 36 733 822 6
.largecircle. .largecircle. 12 317 2.7 350 338 533 35 670 773 6
.largecircle. .DELTA. 12 318 2.4 400 349 546 32 694 792 5
.largecircle. .largecircle. 12 319 3.4 300 253 433 39 559 638 7
.largecircle. .DELTA. 17 320 2.7 350 339 535 36 675 776 6
.largecircle. .largecircle. 12 321 3.4 350 255 443 38 568 647 6
.largecircle. .DELTA. 16 322 2.1 400 377 574 35 726 832 5
.largecircle. .largecircle. 11 323 2.8 350 342 537 35 685 788 6
.largecircle. .DELTA. 12 324 2.6 350 358 555 34 702 805 5
.largecircle. .largecircle. 12 325 2.8 350 293 481 34 615 702 6
.DELTA. .DELTA. 18 326 2.4 350 353 548 35 803 807 6 .largecircle.
.largecircle. 12
[0099]
22 TABLE 22 Mechanical properies Bending Mean Recrystal- Mechanical
properies (Post workpiece) charac- grain lization Proof Tensile
Elonga- Proof Tesile Elonga- teristics Corrosion Electro- Alloy
size temperature stress strength tion stress strength tion (Post
cracking conductivity No. (.mu.m) (.degree. C.) (N/mm.sup.2)
(N/mm.sup.2) (%) (N/mm.sup.2) (N/mm.sup.2) (%) workpiece)
resistance (% IACS) Embodiment 327 2.8 350 329 621 36 655 756 6
.largecircle. .DELTA. 13 3 328 2.8 350 341 536 35 697 792 6
.largecircle. .DELTA. 12 329 2.7 350 343 539 35 680 781 6
.largecircle. .largecircle. 12 330 2.7 350 348 545 32 693 800 5
.DELTA. .DELTA. 12 331 2.5 350 355 551 34 692 804 5 .largecircle.
.largecircle. 12 332 2.4 350 348 543 35 698 802 8 .largecircle.
.largecircle. 12 333 2.5 350 350 545 35 695 796 6 .largecircle.
.DELTA. 13 334 2.6 350 381 557 33 710 818 5 .largecircle.
.largecircle. 12 335 2.8 350 346 545 35 681 790 5 .largecircle.
.largecircle. 11 336 2.8 350 363 556 31 688 806 4 .largecircle.
.largecircle. 11 337 2.7 350 352 542 35 688 796 6 .largecircle.
.largecircle. 12 338 2.3 350 365 559 36 714 826 6 .largecircle.
.largecircle. 12 338A 2.2 640(5) 377 567 37 722 833 7 .largecircle.
.largecircle. 12 339 2.2 350 381 570 37 720 832 7 .largecircle.
.largecircle. 12 340 2.2 350 375 568 38 723 833 6 .largecircle.
.largecircle. 12 341 2.2 350 373 569 36 718 829 6 .largecircle.
.largecircle. 12 342 1.8 400 398 594 34 756 865 4 .DELTA.
.largecircle. 11 343 2.3 350 366 560 34 714 817 6 .largecircle.
.DELTA. 12 344 2.6 350 348 536 36 670 783 5 .largecircle.
.largecircle. 13 345 3.0 350 346 536 32 663 777 4 .DELTA. .DELTA.
12 346 2.4 350 350 545 34 685 780 5 .largecircle. .largecircle. 13
347 2.5 350 363 558 35 702 809 6 .largecircle. .largecircle. 12 348
2.8 350 337 537 33 678 779 5 .largecircle. .largecircle. 12 349 2.4
350 360 558 35 699 814 6 .largecircle. .largecircle. 11 350 2.7 350
333 527 36 669 764 6 .largecircle. .largecircle. 12 351 1.9 400 416
615 31 780 892 4 .DELTA. .largecircle. 11 352 2.5 350 359 551 34
702 810 6 .largecircle. .largecircle. 12 353 2.2 350 367 562 33 720
830 5 .largecircle. .largecircle. 12
[0100]
23 TABLE 23 Mechanical properies Bending Mean Recrystal- Mechanical
properies (Post workpiece) charac- grain lization Proof Tensile
Elonga- Proof Tesile Elonga- teristics Corrosion Electro- Alloy
size temperature stress strength tion stress strength tion (Post
cracking conductivity No. (.mu.m) (.degree. C.) (N/mm.sup.2)
(N/mm.sup.2) (%) (N/mm.sup.2) (N/mm.sup.2) (%) workpiece)
resistance (% IACS) Embodiment 354 2.1 350 377 570 33 725 836 5
.largecircle. .largecircle. 12 3 355 2.1 350 381 572 34 722 836 5
.largecircle. .largecircle. 12 356 2.1 350 375 568 35 733 835 5
.largecircle. .largecircle. 12 357 1.8 350 417 610 31 767 885 4
.DELTA. .largecircle. 11 358 2.4 350 354 548 35 699 804 6
.largecircle. .largecircle. 12 359 2.3 350 364 560 34 727 823 6
.largecircle. .largecircle. 12 360 2.4 350 368 551 34 688 801 5
.largecircle. .DELTA. 12 361 2.4 350 385 556 34 706 811 6
.largecircle. .largecircle. 11 362 2.4 350 377 564 32 708 818 4
.DELTA. .largecircle. 11 363 2.3 350 351 545 34 695 790 6
.largecircle. .largecircle. 12 364 2.9 350 307 480 34 615 698 4
.largecircle. .DELTA. 18 365 3.1 350 335 530 31 653 765 4 .DELTA.
.DELTA. 14 366 2.2 350 377 573 33 724 831 5 .largecircle.
.largecircle. 11 367 3.1 350 297 478 36 612 693 6 .DELTA. .DELTA.
16 368 2.9 300 316 510 37 644 740 6 .largecircle. .largecircle. 12
369 2.7 350 339 540 36 670 783 6 .largecircle. .largecircle. 12 370
2.5 350 344 538 36 681 785 6 .largecircle. .largecircle. 12 371 2.3
350 377 575 34 715 833 5 .largecircle. .largecircle. 11 372 2.4 350
353 548 35 693 804 6 .largecircle. .largecircle. 12 373 2.5 350 354
557 33 700 808 5 .largecircle. .largecircle. 12 374 2.6 350 331 531
35 666 770 6 .largecircle. .largecircle. 12 375 2.8 350 330 523 36
654 758 6 .largecircle. .largecircle. 13 376 2.4 350 354 549 35 705
810 6 .largecircle. .largecircle. 12 377 2.4 350 361 558 35 711 824
6 .largecircle. .largecircle. 12 378 2.3 350 369 567 34 723 832 6
.largecircle. .largecircle. 12 379 2.7 350 334 536 33 676 777 6
.largecircle. .largecircle. 12 380 2.7 350 369 553 33 695 802 4
.DELTA. .largecircle. 12 381 2.4 350 372 566 34 720 831 5
.largecircle. .largecircle. 12
[0101]
24 TABLE 24 Mechanical properies Bending Mean Recrystal- Mechanical
properies (Post workpiece) charac- grain lization Proof Tensile
Elonga- Proof Tesile Elonga- teristics Corrosion Electro- Alloy
size temperature stress strength tion stress strength tion (Post
cracking conductivity No. (.mu.m) (.degree. C.) (N/mm.sup.2)
(N/mm.sup.2) (%) (N/mm.sup.2) (N/mm.sup.2) (%) workpiece)
resistance (% IACS) Embodiment 382 2.5 350 350 545 34 892 791 6
.largecircle. .largecircle. 12 3 383 2.5 350 345 539 36 684 782 6
.largecircle. .largecircle. 12 384 2.1 350 389 585 34 737 859 5
.DELTA. .largecircle. 11 385 2.3 350 354 547 36 698 803 6
.largecircle. .largecircle. 12 386 2.4 350 359 556 35 698 806 6
.largecircle. .largecircle. 12 387 2.4 350 368 562 34 715 829 6
.largecircle. .largecircle. 12 388 3.0 300 338 530 35 681 770 6
.largecircle. .largecircle. 12 389 2.9 300 342 545 35 675 775 6
.largecircle. .largecircle. 12 390 2.7 350 333 527 34 668 760 6
.largecircle. .DELTA. 13 391 2.3 350 372 572 32 720 825 5 .DELTA.
.largecircle. 12 392 2.4 350 370 563 35 725 814 6 .largecircle.
.largecircle. 12 393 2.8 350 354 652 34 685 798 5 .largecircle.
.largecircle. 11 394 2.8 350 353 545 33 673 787 5 .DELTA.
.largecircle. 12 395 2.6 350 352 640 36 678 790 5 .largecircle.
.largecircle. 13 396 1.9 350 408 601 31 755 866 4 .DELTA.
.largecircle. 11 397 2.5 350 360 555 34 703 815 5 .largecircle.
.largecircle. 12
[0102]
25 TABLE 25 Mechanical properies Bending Mean Recrystal- Mechanical
properies (Post workpiece) charac- grain lization Proof Tensile
Elonga- Proof Tesile Elonga- teristics Corrosion Electro- Alloy
size temperature stress strength tion stress strength tion (Post
cracking conductivity No. (.mu.m) (.degree. C.) (N/mm.sup.2)
(N/mm.sup.2) (%) (N/mm.sup.2) (N/mm.sup.2) (%) workpiece)
resistance (% IACS) Comparative 401 6.5 350 136 267 42 345 388 13
.circleincircle. .circleincircle. 56 example 1 402 4.0 350 198 322
44 387 425 14 .circleincircle. .largecircle. 44 403 4.5 350 202 345
44 422 464 14 .circleincircle. .DELTA. 37 404 4.5 350 210 365 45
485 517 12 .largecircle. X 32 405 4.5 300 235 419 46 513 582 10
.largecircle. X 28 406 4.5 300 226 416 42 508 578 8 .DELTA. X 28
407 4.0 350 242 408 40 515 585 7 .DELTA. .DELTA. 28 408 4.0 350 248
388 41 452 490 12 .largecircle. X 25 409 4.5 450 241 368 42 443 485
14 .circleincircle. .circleincircle. 12 410 1.2 400 501 598 36 688
807 5 X X 14 411 1.3 400 438 522 37 612 719 5 X X 17 412 5.5 400
199 328 42 393 436 15 .circleincircle. .circleincircle. 16 413 4.5
350 201 307 44 391 415 16 .circleincircle. .largecircle. 38 414 1.1
400 487 623 36 734 854 4 X .largecircle. 7 415 1.3 450 430 510 35
602 712 6 X .largecircle. 16 416 1.3 450 440 525 34 613 730 5 X
.largecircle. 14 417 1.6 450 366 451 34 573 631 8 X .largecircle.
22 418 1.2 450 465 538 32 630 752 5 X .largecircle. 15 419 1.2 400
448 576 37 647 798 5 X .largecircle. 12 420 2.0 350 357 452 38 535
643 8 X .largecircle. 16 421 -- -- -- -- -- -- -- -- -- -- -- 422
1.6 450 395 470 32 605 678 5 X .largecircle. 26
[0103]
26 TABLE 26 Mechanical properies Bending Mean Recrystal- Mechanical
properies (Post workpiece) charac- grain lization Proof Tensile
Elonga- Proof Tesile Elonga- teristics Corrosion Electro- Alloy
size temperature stress strength tion stress strength tion (Post
cracking conductivity No. (.mu.m) (.degree. C.) (N/mm.sup.2)
(N/mm.sup.2) (%) (N/mm.sup.2) (N/mm.sup.2) (%) workpiece)
resistance (% IACS) Comparative 423 4.5 300 238 419 38 533 609 7
.largecircle. X 28 example 2 424 4.5 300 237 421 36 535 614 6
.largecircle. X 28 425 -- -- -- -- -- -- -- -- -- -- -- 426 2.8 350
333 537 28 685 753 2 X X 13 427 -- -- -- -- -- -- -- -- -- -- --
428 2.7 350 338 546 27 688 748 2 X X 13 429 4.0 350 246 448 37 572
645 7 .largecircle. X 20 430 2.9 350 363 540 29 685 766 2 X .DELTA.
12 431 -- -- -- -- -- -- -- -- -- -- --
INDUSTRIAL APPLICABILITY
[0104] As understood from Tables 15 to 26, in comparison with first
and second comparative example alloys having neither alloy
composition nor recrytallized structure specified at the beginning,
it becomes possible for the first to third invention copper alloys
to realize the grain refinement and to improve greatly the
machinability and bending characteristics. It is possible for the
present invention alloy to be used preferably as plate, rod and
wire materials even in difficult applications in which the prior
high strength copper alloy cannot be used. In addition, it is
possible to obtain the grain refinement and strength improvement by
the recrystallization treatment due to the rapid high temperature
heating processes. Furthermore, though not shown in Tables 15 to
26, as regards said post workpiece (pieces that the cold rolling
and wire drawing are performed additionally for the rolled stock
and wire drawing material after the recrystallization) heat-treated
for 1 second to 4 hours at 150 to 600.degree. C., it was confirmed
that spring deflection limit and stress relaxation characteristics
are greatly improved.
* * * * *