Note: Descriptions are shown in the official language in which they were submitted.
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COPPER TIN NICKEL PHOSPHORUS ALLOYS WITH IMPROVED STRENGTH AND FORMABILITY
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional Patent
Application Serial No. 60/979,064, filed October 10, 2007, the entire
disclosure
of which is incorporated herein.
BACKGROUND
[0002] This invention relates to copper alloys, and in particular to
copper-tin-nickel-phosphorus alloys with improved strength and formability.
[0003] There is a continued need for high strength copper alloys of
good formability and reasonable cost for use in electrical connectors, and in
particular for use in automotive electrical connectors. Current connector
alloys in the low cost Cu-Sn-Ni-P family lack the combination of properties of
practical strength (77 KSI), intermediate conductivity (37 %IACS), excellent
formability, and decent stress relaxation (65% at 150 C). Formability in the
document is measured by forming a strip by roller bending it 90 - about a die
of known radii. The ratio of the smallest die radii that the strip can be
formed
without cracking is divided over the strip thickness. Bends were measured
both parallel (bad way, BW) and perpendicular (good way, GW) to the
direction of rolling. Table 1 shows currently available Cu-Sn-Ni-P alloys:
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Table 1: Available connector alloys in the Cu-Sn-Ni-P family
Alloy Yield Conductivity Bends __ Stress
(Company) Strength (%IACS) 90 GW 90 BW relaxation
(KSJ) ( /%SR @
150 C
C19025 76 40 0.8 1 77%
(Olin)
C19020 67 50 0.8 1.0 75%
(Olin)
C19500 77 40 1.5 1.5 54%
(Olin)
C19210 60 90 0.5 1.5
PMX
C18665 67 60 1,0 2.0 *
(KME,
Mitsubishi)
C50715 77 35 0.5 0.5 *
(Kobe)
C50725 77 33 0.5 0.5 *
(Kobe)
C198 69 60 0.5 0.5
(Kobe)
C40820 80 35 S S *
(Kobe)
[0004] C19025 comes close to achieving the desired properties but
lacks the strength with acceptable formability; 040820 has the strength and
superior formability but does not have the electrical conductivity.
SUMMARY
[0005] Embodiments of the present invention provide a copper-tin-
nickel-phosphorus alloy with an improved combination or properties, and in
particular improved combination of yield strength and formability. In one
preferred embodiment the alloy comprises between about 1% and about 2%
Sn; between about 0.3% and about 1 %Ni; between about 0.05% and about
0.15% P, and at least one of between about 0.01% and about 0.20% Mg and
about 0.02% and about 0.4% Fe, the balance being copper. The addition of
iron can be used as a low cost substitute for of Mg if good stress relaxation
is
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not required for the application. More preferably the alloy comprises between
about 1.1% and about 1.8% Sn, between about 0.4% and about 0.9% Ni,
between about 0.05% and about 0.14% P, and between about 0.05 and about
0.15 Mg. Fe may be substituted for some of the Mg. Most preferably the
alloy comprises, between about 1.2% and about 1.5% Sn; between about
0.5% and about 0.7%Ni; between about 0.09% and about 0.13% P, and
between about 0.02% and about 0.06% Mg, the balance being copper. The
alloy is preferably processed to have a yield strength of at least about 77
KSI,
electrical conductivity of at least about 37 %IACS, and formability (90
GW/BW) of 1.0/1Ø The alloy preferably also has a stress relaxation of 65%
at 150 C.
[0006] The Sn gives the alloy solid solution strengthening. Ni and
Mg are added to form precipitates of phosphorus with the added benefit of Mg
increasing strength without lowering the electrical conductivity. The metal
(Ni+Mg) to P ratio (the M/P ratio) is preferably controlled to a range of 4 to
8.5. If the ratio falls below 4 strengthening is not obtained and if is
greater
that 8.5 the material does not achieve 40% IACS.
[0007] In accordance with the preferred embodiment of this
invention, the alloy is processed by melting and casting, hot rolling from
about
850 C to about 10002C cold rolling up to about 75% annealing between
about 450 C - about 6002C, cold rolling up to about a 60% reduction
followed by annealing at 425 2C to about 6002C, cold rolling to about 50%
prior to the final anneal between about 400 C and 550 -C. A final cold roll
reduction is given to achieve the desired thickness and mechanical strength
prior to a thermal stress relief treatment. In another preferred embodiment
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the processing includes a double final anneal treatment and the elimination of
an upstream anneal which improves formability and strength respectively.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] Fig. 1 is a photomicrograph of the alloy in Example 1;
[0009] Fig. 2 is a graph showing the relationship between YS and
MIP ratio, and illustrating the preferred M/P ratio for a Cu-Sn-Ni-P-Mg alloy;
[0010] Fig. 3 is a graphs showing the relationship between %IACS
and M/P ratio, and illustrating the preferred M/P ratio of 4-8.5 ratio for a
Cu-
Sn-Ni-P-Mg alloy;
[0011] Fig. 4A is a flow chart of a preferred embodiment of a
method of processing alloys in accordance with the principles of the present
invention;
[0012] Fig. 4B is a flow chart of an alternate preferred embodiment
of processing alloys in accordance with the principles of this present
invention;
[0013] Fig. 4C is a flow chart of an alternate preferred embodiment
of processing alloys in accordance with the principles of this present
invention; and
[0014] Fig. 5 is a photomicrograph of an alloy 4 after double
anneal, showing a grain size of between 6 - 7 pm, with some areas appearing
to have not fully recrystallized grains; and
[0015] Fig. 6 is a photomicrograph of an alloy 4 from the process 3
after strip anneal, showing a grain size of 4 - 5 pm.
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DETAILED DESCRIPTION
[0016] Embodiments of the present invention provide a copper-tin-
nickel-phosphorus alloy with an improved combination or properties, and in
particular improved combination of yield strength and formability. In one
preferred embodiment the alloy comprises between about 1% and about 2%
Sn; between about 0.3% and about 1%Ni; between about 0.05% and about
0.15% P, and at least one of between about 0.01% and about 0.20% Mg and
about 0.02% and about 0.4% Fe, the balance being copper. The addition of
iron can be used as a low cost substitute for of Mg if good stress relaxation
is
not required for the application.
[0017] More preferably the alloy comprises, between about 1.2%
and about 1.5% Sn; between about 0.5% and about 0.7%Ni; between about
0.09% and about 0.13% P, and between about 0.02% and about 0.06% Mg,
the balance being copper. The alloy is preferably processed to have a yield
strength of at least about 77 KSI, electrical conductivity of at least about
37
%IACS, and formability (90 GW/BW) of 1.0/1Ø The alloy preferably also
has a stress relaxation of 65% at 150 C.
[0018] The Sn gives the alloy solid solution strengthening. Ni and
Mg are added to form precipitates of phosphorus with the added benefit of Mg
increasing strength without lowering the electrical conductivity. The M/P
ration is preferably controlled to a range of 4 to 8.5. If the ratio falls
below 4
strengthening is not obtained and if is greater that 8.5 the material does not
achieve 40% IACS.
[0019] In accordance with the preferred embodiment of this
invention, the alloy is processed by melting and casting, hot rolling from 850-
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1000 -C cold rolling up to about 75% annealing between 450- 6000C, cold
rolling about 60% followed by annealing at 425-6002C, cold rolling about 50%
prior to the final anneal between 400-550 -C. A final cold roll reduction is
given to achieve the desired thickness and mechanical strength prior to a
thermal stress relief treatment. In another preferred embodiment the
processing includes a double final anneal treatment and the elimination of an
upstream anneal which improves formability and strength respectively.
Example 1
[0020] A series of 10 pound laboratory ingots with the compositions
listed in Table 2 were melted in silica crucibles and cast into steel molds
which were after gating 4"x4"x1.75". After soaking for 2 hours at 9009C they
were hot rolled in three passes to 1.1" (1.6"/1.35/1.1"), reheated at 900 C
for
minutes, and further reduced by hot rolling in three passes to 0.50"
(0.9"/0.7/0.5"), followed by a water quench. After trimming and milling to
remove the surface oxide, the alloys were cold rolled to 0.120" and annealed
at 570 C for 2 hours. The alloys were cleaned and cold rolled to 0.048" and
annealed at 525 C for 2 hours. The alloys were cold rolled to 0.030" and
annealed at 5009C for 2 hours. The final cold roll was 60% to 0.012" and a
stress relief heat treatment was performed at 2500C for 2 hours.
Table 2: Allo s and properties from Example 1
ALLOY %Sn %Ni %P YS" EL% IACS% 90GW 90BW Ni/P
K242 0.92 0.26 0.008 65.3 8.29 51.3 nm nm 32.50
K243 1.33 0.26 0.014 68.65 9.54 42.6 nm nm 18.57
K244 0.9 0.27 0.12 70.85 10.46 38.4 1.33 1.5 2.25
K245 1.27 0.28 0.11 74.65 11.06 34.6 nm nm 2.55
K246 0.9 0.69 0.01 67.65 7.5 44 nm nm 69.00
K247 1.33 0.7 0.005 70.2 8.2 39.7 1.67 2.33 140.00
K248 0.91 0.71 0.1 75 9.455 46.5 1.32 2.25 7.10
K249 1.25 0.7 0.091 79.2 10.05 40.8 1.33 2.5 7.69
K250 1.06 0.48 0.052 74.1 9.515 43.6 1.33 2.17 9.23
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*for this Table and throughout this document YS means Yield Strength and is
given in units of KSI
From the data in Example 2, it was determined that the Ni level is preferably
at
least 0.5 and the best overall alloys had a Ni/P ratio of 7-9. All the bends
were
poor due to the presence of contamination of sulfur forming long stringers as
shown in Figure 1.
Example 2
[0021] A series of 10 pound laboratory ingots with the compositions
listed in Table 3 were melted in silica crucibles and cast into steel molds
which were after gating 4"x4"x1.75". After soaking for 2 hours at 9002C they
were hot rolled in three passes to 1.1" (1.6"/1.35/1.1"), reheated at 900 -C
for
minutes, and further reduced by hot rolling in three passes to 0.50"
(0.9"10.7/0.5'"), followed by a water quench. After trimming and milling to
remove the surface oxide, the alloys were cold rolled to 0.120" and annealed
at 5702C for 2 hours. The alloys were cleaned and cold rolled to 0.048" and
annealed at 5252C for 2 hours. The alloys were cold rolled to 0.024" and
annealed at 4502C for 8 hours. The final cold roll was 50% to 0.012" and a
stress relief heat treatment was performed at 2500C for 2 hours.
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Table 3- Alloys from Example 2.
4500/8HRS -Single Anneal
ALLOY YS EL% WAGS 90GW 9OBW Sn Ni P Fe M 1V
K279 invalid 9.41 51.2 1.00 1.17 1.07 0.41 0.048 0 0 8
K280 71.4 8.08 51 0.99 0.99 0195 0.45 0.054 0 0 8
K281 72 11.84 50.4 1.17 1.33 0.98 0.53 0.063 0 0 8
K282 71.4 11.81 49.4 1.17 1.33 1.03 0.62 0.063 0 0 9
K283 71 10.68 47.9 1.17 1.17 0.99 0.71 0.048 0 0 1.
K284 70.7 11.66 51.9 1.17 1.17 0.9 0.54 0.072 0 0 7
K285 73.5 10.33 48.9 1.17 1.00 1.11 0.54 0.067 0 0 8
K286 73.9 7.31 50.4 1.16 0.99 0.96 0.53 0.095 0 0.038 5
K287 75.5 10.75 49.8 0.99 0.99 1.06 0.56 0.12 0 0.049 5
K288 74.1 10.7 50.2 1.17 1.00 0.99 0.53 0.096 0 0.058 6
K289 69.3 8.61 54.9 1.34 1.34 1 0 0.032 0 0.058 1
K290 71.7 9.93 52.8 1.15 1,15 1 0 0.045 0 0.14 3
K291 74.4 10.88 50.5 1.16 1.32 1.1 0 0.095 0.38 0 4
K292 74.1 10.06 51.5 1.00 1.00 1.05 0 0.105 0.17 0,06= 2
K293 76.8 10.9 42.2 0.99 1.32 1.55 0.72 0.092 0 0 7
K294 80 10.62 38.4 0.99 1.16 1.79 1 0.098 0 0 11
In general the strengths are low with the exception of alloys K293 and K294.
Both these alloys contained more Sn than any of the others by about 0.5%
correlating higher Sn levels to higher strength. The strengths of K286, K287
and
K288 indicate the benefit of Mg as opposed to alloys of very close composition
but without Mg, K282 and K284. It is notable that there is no drop in
conductivity
(the %IACS) accompanying the increase in yield strength. There was an
increase in strength with the addition of iron to K291 and Mg in K289 both
without
Ni. The conductivity for the iron containing alloy is lower than the Mg
containing
alloy by about 4 %IACS. Both of these alloys are almost perfectly balanced;
Mg/P ratio is 1.81 for K289 close to the ideal of 1.2 and the Fe/P ratio for
K291 is
4.00 which is also close to the ideal of 3.6. Iron is a more effective
strengthener
but leads to lower conductivity.
Example 3
[0022] A series of 10 pound laboratory ingots with the compositions
listed in Table 4 were melted in silica crucibles and cast into steel molds
which were after gating 4"x4"x1.75". After soaking for 2 hours at 900 -C they
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were hot rolled in three passes to 1.1" (1.6"/1.35/1.1"), reheated at 9002C
for
minutes, and further reduced by hot rolling in three passes to 0.50"
(0.9"/4.7"70.5"), followed by a water quench. After trimming and milling to
remove the surface oxide, the alloys were cold rolled to 0.120" and annealed
at 5702C for 2 hours. The alloys were cleaned and cold rolled to 0.048" and
annealed at 5252C for 2 hours. The alloys were cold rolled to 0.024" and
annealed at 4509C for 4 hours only for the single anneal condition and for
4509C for 4 hours plus 375 C for another 4 hours constituting the double
anneal condition. The final cold roll was 50% to 0.012" and a stress relief
heat treatment was performed at 2502C for 2 hours for both conditions.
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Table 4- Alloys from example 3 including both annealing conditions.
Single Anneal 45OC14hrs
ALLOY SN NI P FE MG ZN YS EL% IACS% 90GW 908W
K310 1.54 0.51 0.042 0 0 0 74.9 13.36 38.5 0.85 1.69
K311 1.57 0,47 0,054 0 0 0.73 77.4 12.83 36.9 1.00 1.67
K312 1.64 0.53 0.167 0.41 0 0 82.2 11 37.2 0.83 1.00
K313 2.17 0.5 0.163 0.17 0 0 86.6 9.29 33.6 0.67 1.50
K314 1.58 0.500 0.136 0 0.052 0 81.4 13.72 38.1 0.83 1.00
K315 2.1 0.52 0.138 0 0.053 0 85 14.41 34 0.33 1.30
K316 1.57 0.52 0.13 0 0.049 0 82 11.09 39 0.66 0.82
K317 2.03 0.53 0.13 0 0.043 0 85.2 11.4 33.4 0.17 1.19
K318 1.59 0.5 0.073 0 0.059 0 78.4 10.42 38.5 0.83 1.16
K319 0.56 0.98 0.007 0 0 0 62 9.23 46.5 1.51 1.34
K320 0.93 0.98 0.025 0 0 0 68.5 6.34 40.8 1.03 1.03
K326 1.57 0.67 0.086 0 0 0 77.7 13.6 38.3 0.84 1.01
K327 1.54 0.69 0.127 0 0.032 0 79.1 11.49 38.8 0.84 1.01
Double anneal 450c14hrs + 375C/4hrs
ALLOY SN NI P FE MG ZN YS EL%a IACS% 90GW 90BW
K310 1.54 0.51 0.042 0 0 0 75 13.01 38.5 0.50 2.33
K311 1.57 0.47 0.054 0 0 0.73 77.3 12.7 37.1 0.33 1.64
K312 1.64 0.53 0.167 0.41 0 0 82.5 11.29 37.6 0.25 0.49
K313 2.17 0.5 0.163 0.17 0 0 87.4 13.03 34.1 0.17 0.66
K314 1.58 0.500 0.136 0 0.052 0 81.8 12.92 40 0.33 0.83
K315 2.1 0.52 0.138 0 0.053 0 85 13.52 34.2 0.66 0.82
K316 1.57 0.52 0.13 0 0.049 0 81.3 14.23 39.5 0.50 0.83
K317 2.03 0.53 0.13 0 0.043 0 85.3 11.63 33.8 0.17 0.50
K318 1.59 0.5 0.073 0 0.059 0 78.3 11.86 38.7 0.34 0.50
K319 0.56 0.98 0,007 0 0 0 62.6 4.91 46.6 0.10 1.34
K320 0.93 0.98 0.025 0 0 0 68.9 6.87 41.5 0.33 0.33
K326 1.57 0.67 0.086 0 0 0 78.2 12.16 38.5 0.10 0.82
K327 1.54 0.69 0.127 0 0.032 0 79.3 12.37 39.7 0.66 0.99
Higher Sn levels helped the strength levels considerably but at lower
conductivities. Compare alloys K320 and K319; 7KSI difference in YS and
3%IACS in conductivity. The trend holds for those alloys with iron (K312 and
K313) and those with magnesium (K 314 and K315) although the impact on
strength is less than those without any other addition. There was no overall
advantage of zinc K311 in contrast to K310; strength is increased but with
lower
conductivity. The double anneal showed an increase in formability (i.e., a
decrease in the 90 bend radii that can be achieved). Slight increases in the
conductivities are also noted.
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Example 4
[0023] A series of 10 pound laboratory ingots with the compositions
listed in Table 4 were melted in silica crucibles and cast into steel molds
which were after gating 4"x4"x1.75". After soaking for 2 hours at 9000C they
were hot rolled in three passes to 1.1" (1.6'71,35/1.1"), reheated at 900 -C
for
minutes, and further reduced by hot rolling in three passes to 0.50"
(0.9'70.770.5"), followed by a water quench. After trimming and milling to
remove the surface oxide, the alloys were cold rolled to 0.120" and annealed
at 570 -C for 2 hours. The alloys were cleaned and cold rolled to 0.048" and
annealed at 525 C for 2 hours. The alloys were cold rolled to 0.024" and
annealed at 450 C for 4 hours only plus 375"C for another 4 hours. The final
cold roll was 50% to 0.012" and a stress relief heat treatment was performed
at 2509C for 2 hours.
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Table 5. Data from example 4
ALLOY YS EL% IACS% 90GW 90BW SN NI P FE MG M
K335 71.5 11.41 42.4 0.26 0.26 1.13 0.52 0.086 0 0 6.1
K336 71.2 9.93 41.4 0.34 0.17 1.28 0.69 0.053 0 0 13
K337 72.5 12.08 41.7 0.08 0.17 1.46 0.51 0.075 0 0 6.K338 76.3 12.78 38.2 0.08
0.25 1.38 0.53 0.099 0.37 0 9.
K339 78.9 11.99 36.6 0.08 0.67 1.7 0.53 0.105 0.33 0 8.
K340 73.6 12.66 41.4 0.17 0.50 1.45 0.52 0.079 0 0 6.
K341 73.5 11.79 39.1 0.17 0.34 1.47 0.69 0.064 0 0 10
K342 73.5 11.76 41.7 0.25 0.16 1.43 0.53 0.067 0 0 7.
K343 75.2 12.77 38.4 0.08 0.33 1.71 0.53 0.08 0 0 6.
K344 71.9 10.51 38 0.67 0.67 1.67 0.52 0.033 0 0 15
K345 74.8 11.84 38.6 0.08 0.17 1.61 0.69 0.076 0 0 9.
K346 74.8 10.02 38.4 0.08 0.08 1.35 0.32 0.105 0.4 0 6.
K347 76.5 10.58 41.4 0.08 0.17 1.38 0.3 0.143 0.23 0 3.
K348 75.4 12.48 32.8 2.00 3.00 1.71 0.32 0.139 0 0 2.
1(349 70.5 12.53 41.5 0.50 0.50 1.35 0.53 0.035 0 0 15
K350 76.3 13.37 38.1 0.17 0.25 1.62 0.7 0.081 0 0.031 9.
K351 76.3 10.72 40.6 0.08 0.33 1.35 0.69 0.092 0 0.049 8.
K352 75.8 12.55 41 0.17 0.17 1.37 0.54 0.129 0 0.021 4.
K355 78.7 13.83 37.1 0.25 0.50 1.74 0.32 0.145 0.21 0 3,
1(356 75.6 11.99 41.5 0.67 0.67 1.42 0.54 0.09 0 0.041 7.
K361 78.7 15.11 34.2 0.34 0.50 1.7 0.33 0.151 0.043 0 2
Thirteen of the twenty-two alloys in this group had yield strengths of 75 KSI
or
above. Six contained iron (K338, K339, K345, K346, K355 and K361) none of
which made electrical conductivity of 40%IACS, although K338 is the closest at
38%IACS. Four contained Mg (K350, K351, K352 and K356) and 3 of these 4
exceeded 40%IACS. Note that K350 which did not achieve 40%IACS had a
metal to phosphorus ratio of 9, greater that the recommended 8.5. Three of the
alloys with yield strengths of 75 ksi or greater contained neither iron nor Mg
(K343, K345, and K348), but none of these alloys had conductivities of
40%IACS.
Example
[0024] All the data for Mg containing alloys and Mg-free alloys are
combined in Tables 6 and 7. These data are from example 2, (Table 3 alloys
which were double annealed and included in Tables 6 and 7), Example 3
(Table 4), and Example 4 (Table 5), and include data from Example 3. The
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process used for all the alloys is identical to the process used in the final
double anneal of 4 (or 8 hours; see note) at 450 C+ 4 hours at 375 C.
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Table 6. Grouped data from Examples with Mg, all double annealed
a- 00 co - r (0 co Ca m DJ 0, ) CD
rn Q co;: q) cr) co n n c~ v
LO L6 6 -: V5 4 4 r-, L6 a) co 4 <6
co Cco CO N CCAN 0)
co -r LC) LO LC} V' LO Cr) C') <t 04 'et'
Q Q Q Q r g q n n Q Q (õ)
0d00n 0 Cac ciQca ~"yt)
r1
C")
CS)
O
0 Q n 010 0 0 0 Q 0 0 0 0
+
L() CONLO CO C]i~YNa)
0 0 0 0 d ci a ca ci n
co
(D c) LNn
u) ~~Lr"iL~yn q)
LnLnnn,~ CD
000 '50000000 LID
d
n
(0(00 ODN N LD N.N C
Cri n a7 .- ,- 19 LC'y LC) CO (c) d; Cd
n
~~~~ ~nDODtoQMMN
Y r C7 r-^ r 0 0 Ca r Ca O Ca C ..C,
C
C[)
~tn..Q~CN0.7C-jLClf')NN E
Q rrr .-0000000 C ~'*
0)
e)
C)
~rnn~t CDQ~~r~ ~n
0) ~r 0) 0) CO 0) (0 0
TLO LI)LC) co 0)C')C') V
Ca
c~yy 0)
o N W cm aNY
N N W C~*) C~'J LO
C~
r e-^ r '- ems- Y CV @a n N
C_
C7
CD0 NOR 0chc+7 c') c! cC 0 _C7)
I- N- N- Co W CO ~ r ~ r- r-
t~
C
0) C) - 0) OR W r: r,% CA
IvtiNr -fl-i 0C C)CO
co C) CO CO n N r`- E` Q
0
CDN 0)(n 0 "4- CO OD N0 NCD
C) LC) tt,,([yy
0 i.: CC3 C4
N CD (0V C0N ) r C+) N Ch L0 L C7 Ch
N
Q~Y`C`..GXYYYYYYYY
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Table 7. Grouped data from all Examples without Mg, all double annealed
ALLOY TS YS EL% SiGMA 90GW 9OBW Sn Ni P Mg Ni/P
K279 74 71.8 8.61 511 1.1 1.1 1.07 0.41 0.048 0 8.54
K280 73.3 71.6 9.36 50.7 1.0 1.1 0.95 0.45 0.054 0 8.33
K281 74.7 73 10.9 51 1.0 1.2 0.98 0.53 0.063 0 8.41
K282 73.5 71.8 9.41 49.2 1.5 1.5 1.03 0.62 0.063 0 9.84
K283 73.2 71.2 7.96 47.9 1.2 1.2 0.99 0.71 0.048 0 14.79
K284' 725 70.5 7.92 51.7 1.0 1.0 0.9 0.54 0.072 0 7.50
K285 75.4 73.2 11.8 49 1.2 1.3 1.11 0.54 0.067 0 8.06
K293 81.5 79.2 10.44 427 1.3 1.3 1.55 0.72 0.092 0 7.83
K294 83.3 81.3 10.78 38.5 1.1 1.3 1.79 1 0.098 0 10.20
K310 77.5 75 13.01 38.5 0.5 2.3 1.54 0.51 0.042 0 12.14
K319* 63.7 62.6 4.91 46.6 0.1 1.3 0.56 0.98 0,007 0 140.00
K320* 70.4 68.9 6.87 41.5 0.3 0.3 0.93 0.98 0.025 0 39.20
K326 80.7 78.2 12.16 38.5 0.1 0.8 1.57 0.67 0.086 0 7.79
K335 76.5 71.5 11.41 42.4 0.3 0.3 1.13 0.52 0.086 0 6.05
K336 75.2 71.2 9.93 41.4 0.3 0.2 1.28 0.69 0.053 0 13,02
K337 76.9 72.5 12.08 41.7 0.1 0.2 1.46 0.51 0.075 0 6.80
K340 77.2 73.6 12.66 41.4 0.2 0.5 1.45 0.52 0.079 0 6.58
K341 76.7 73.5 11.79 39.1 0.2 0.3 1.47 0.69 0.064 0 10.78
K342 77 73.5 11.76 41.7 0.2 0.2 1.43 0.53 0.067 0 7.91
K343 79.2 75.2 12.77 38.4 0.1 0.3 1.71 0.53 0.08 0 6.63
K344 75.5 71.9 10.51 38 0.7 0.7 1.67 0.52 0.033 0 15.76
K345 78.7 74.8 11.84 38.6 0.1 0.2 1.61 0.69 0.076 0 9.08
K348 80.9 75.4 12.48 32.8 2.00 3.00 1.71 0.32 0.139 0 2.37
K349 73.7 70.5 12.53 41.5 0.5 0.5 1.35 0.53 0.035 0 15.14
`Alloys K 319 and K320 are similar to C19020 and C19025, but with lower P.
Alloys in highlighted in light gray had a slightly different final double
anneal 4502C for 8
hours + 4 hours at 375 -C
[0025] Overall the YS in Table 6 with Mg are higher than those in
Table 7 without Mg. Only a few Mg-free alloys reach a minimum YS of 75
KSI: K293, K294, K310, K326, K343, K345, and K348, with corresponding
electrical conductivities of: 42.2, 38.5, 38.5, 38.5, 38.4, 38.6 and 32.8
%IACS
respectively. Note with the exception of K293 none of the alloys achieve
40%IACS. Alloys K293, K294 and K326 all have properties of YS and
conductivities close to C19025 but have better bends. In contrast the Mg
alloys in Table 6 all have YS of at least 75 KSI with the exception of K289
and
K290 (which had no Ni and an M/P ratio below 4). The electrical
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conductivities of all the alloys are at or above 40%IACS except for K318 (38.7
%IACS) with an M/P of 7.66 and K350 (38.1 %IACS) with an M/P ratio of
9.02. As the metal to phosphorus ratio increases the conductivity decreases
and the combination of desirable properties becomes more difficult to reach.
The addition of Mg enables the combination of yield strength over 75 KSI and
conductivity of at least 40 %IACS achievable when employing appropriate
processing and maintaining an M/P ratio between 4 and 8.5. Figures 2 and 3
illustrate the relationships between the ratios and YS and %IACS respectively.
The vertical lines in Figs. 2 show the preferred M/P ratio of 4-8.5.
Example 7
[0026]A series of 10 pound laboratory ingots with the compositions
listed in Table 8 were melted in silica crucibles and cast into steel molds
which were after gating 4"x4"x1.75". After soaking for 2 hours at 9009C they
were hot rolled in three passes to 1.1" (1.6"/1.35/1.1"), reheated at 900 -C
for
minutes, and further reduced by hot rolling in three passes to 0.50"
(0.9"/0.7"/0.5"), followed by a water quench. After trimming and milling to
remove the surface oxide, the alloys were cold rolled to 0.080" and annealed
at 550 C for 2 hours. The alloys were cleaned and cold rolled to 0.036" and
annealed at 4500C for 4 hours only plus 375 C for another 4 hours. The final
cold roll was 60% to 0.012" and a stress relief heat treatment was performed
at 250 C for 2 hours.
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Table 8. Data from Example 7
ALLOY TS YS EL% IACS% 90GW 9OBW SN NI P MG Metal/P
K340 84.4 81.2 9.72 41.2 0.2 1.0 1.45 0.52 0.079 0 6.58
K341 84.1 80.9 12.16 39.2 0.3 1.2 1.47 0.69 0.064 0 10.78
K350 87.6 84.4 14.24 37.3 0.1 0.8 1.62 0.7 0.081 0.031 9.02
K352 87.6 83.8 11.58 41 0.2 1.3 1.37 0.54 0.129 0.021 4.35
Increased cold work improved strength for all alloys. However, the Mg
containing
alloy with an M/P ratio below 9 (K352) was the only one to improve YS while
maintaining or improving conductivity.
Example 8
[0027]A series of 10 pound laboratory ingots with the compositions
listed in Table 3 were melted in silica crucibles and cast into steel molds
which were after gating 4"x4"x1.75". After soaking for 2 hours at 9002C they
were hot rolled in three passes to 1.1" (1.6"/1.35/1.1"), reheated at 900 C
for
minutes, and further reduced by hot rolling in three passes to 0.50"
(0.970.7"10.5"), followed by a water quench. After trimming and milling to
remove the surface oxide, the alloys were cold rolled to 0.120" and annealed
at 5702C for 2 hours. The alloys were cleaned and cold rolled to 0.048" and
annealed at 5259C for 2 hours. The alloys were cold rolled to 0.024" and
annealed at 450 -C for 4 hours minimum. The final cold roll was 50% to
0.012" and a stress relief heat treatment was performed at 2500C for 2 hours.
The samples were subjected to stress relaxation testing at 150 C for
1 000hrs. The results are given in Table 9 below:
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Table 9. Data from Example 8
Alloy Composition %Stress
Remaining
K291 Cu-1.1Sn-0.38Fe-0.095P 56.6
K312 Cu-1.64Sn-0.53Ni-0.41Fe-0.167P 58.7
K314 Cu-1.58Sn-0.50Ni-0.052Mg-0.136P 66.8
Alloys K291 and K312 with iron did not maintain 60% of the initial stress. The
results are similar between the two despite the presence of Ni in K312. K314
with Ni and Mg combination maintained more than 65% of the initial stress.
Example 9
[0028] A set of Mg and Mg-free alloys were processed using the
indicated schedules. Tables 10 and 11 summarize the results. Both sets of
alloys
achieved yield strengths over 80 KSI. The Mg-containing alloys, all exceeded
the
target conductvity of 38% IACS, whereas the Mg-free alloys, with the exception
of
K412, did not. In addition, the formability of the Mg-containing alloys was
generally
better.
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Table 10 Summary of Results for Mg-Containing alloys
ALLOY YS EL% %IACS 90GW 9OBW Sn Ni P Mg Metal/P
K373 80.3 11.69 43.7 0.50 1.01 1.13 0.5 0.077 0.016 6.70
K374 81 11.17 42.9 0.17 1.0o 1.17 0.71 0.085 0.01 8.47
K375 83.3 13.17 38.8 0.08 1.33 1.54 0.7 0.091 0.014 7.85
K376 83 11.14 39.1 0.17 1.00 1.52 0.52 0.104 0.017 5.16
K351 83.8 10.45 40.9 0.17 0.83 1.35 0.69 0.092 0.049 8.03
K356 82.1 10.57 42.4 0.08 1.01 1.42 0.54 0.09 0.041 6.46
K394 87.6 10.13 39.9 0.08 0.83 1.41 0.51 0.16 0.06 3.56
K395 84.1 9.81 43.3 0.08 0.83 1.27 0.5 0.06 0.055 9.25
K399 84.7 12.78 39.9 0.25 2.33 1.42 0.5 0.094 0.042 5.77
K400 84.9 10 39.4 0.08 1.18 1.61 0.51 0.159 0.044 3.48
6
K401 82.7 9.53 38.4 0.08 0.67 1.54 0.71 0.074 0.02 9.8
K402 87.2 11.09 39.4 0.08 0.83 1.51 0.71 0.11 0.028 6.71
YS is in KSI
Process Details: HRP + CR to 0.060 gage + 500 C/8hrs + CR 50% to 0.030 gage +
450 CI4hrs + 375 C/4hrs + CR 60% to 0.012 gage + 250 C/2hrs
Table 11 Summary of Results for the Mg-free alloys
Alloy YS EL% IACS% 90GW 90BW Sn Ni P Ni/P
K378 86.3 12.58 37.8 0.98 1.48 1.5 0.99 0.12 8.25
K412 83.1 12.88 39.5 0.99 1.32 1.6 0.49 0.05 9.80
K413 83.4 12.44 35.9 0.83 1.17 1.65 1.1 0.048 22.92
K414 83.3 10.4 35.8 0.85 1.69 1.89 0.48 0.03 16.00
K415 85.7 12.36 37.1 0.08 1.67 1.9 0.48 0.08 6.00
K416 86.1 7.35 32.6 0.25 1.51 1.93 1.1 0.044 25.00
YS is in KSI
Process Details: HRP + CR to 0.060 gage + 475 C/16hrs + CR 50% to 0.030 gage +
450 C14hrs + 375 C/4hrs + CR 60% to 0.012 gage + 250 C/2hrs
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Example 10
[0029] Plant processing was conducted on six alloys whose nominal
compositions are set forth in Table 12. The processes are detailed in Table
13,
where Process 1 is a laboratory process for comparison purposes, and
Processes 2, 3, and 4 are plant processes.
Table 12 Chemistry of Plant-Processed Bars
Alloy
Sn Ni P M
1 1.64 0.88 0.074 0
2 1.7 0.65 0.1 0
3 1.39 0.65 0.1 0.035
4 1.42 0.68 0.11 0,038
1.66 1 0.1 0
1 6 0.91 0.98 0.056 0
[0030] The chemistry given in the Table 12 is the analyzed chemistry
for the cast bars. Alloy 6 lies within the CDA range for C19025 and is present
as
a comparative example. All alloys were processed the same way: They were all
hot rolled from 900 C, coil milled and then cold rolled to 0.125 or 0.100
gauge.
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Table 13 Definition of Processes for Example 10
Process l Process 2 Process 3 Process 4
HR HR+CR----*0.100 HR+CR-}0.125 HR+CR->0.125
CR-0.060 CR---X0.060
Anneal500 C/8hr Anneal500 C Anneal520 C Annea1520 C
to adequately to adequately to adequately
recrystalize recrystalize rec stalize
CR->0.030 CR-}0.0295 CR-0.0295 CR---40.0513
450 /6h+25 C/h slow 570 C 580 C
450 C/4h+375 CI4h cool to 375 C/5.5h
CR-- 0.012 CR-X0.0118 CR-+0.0118 CR-->0.0118
250 C/2h 400 C 400 C 400 C
The resulting properties at final gage are shown in Table 14. Alloy 6
processed using
Processes 3 and 4 possessed the expected properties for this alloy, having
higher yield
strength and poorer bends for Process 4 versus Process 3. Alloy 5 had a lower
yield
strength (YS) and poorer bad way bends when processed according to Process 2
in
contrast to the Process 3 metal. Alloy 3 had comparable yield strength and
conductivity
for both the Process 2 and Process 3 processing but metal processed according
to
Process 3 had better bad way bends.
Table 14 Results from the Plant Trial as Compared to the Laboratory Processed
Metal
Alloy Process 2 Process 3 or 4* Process 1
Results YS IACS GW BW YS IACS GW BW YS IACS OW 71
Alloy 6 77.2 41.5 0.17 1.36
- - - - 75.3 41.6 0.09 0.88 - - - -
- - - - 79* 41.4* 0.18* 1.67* - - - -
Alloy 5 82.6 35.4 0.08 1.27 85.3 34.8 0.08 1.03 - - - -
Alloy 1 80.5 35.4 0.08 1.11 - - - -
81.0 36.6 0.08 O.E
Alloy 2 81 37.4 0.08 0.94 - - - - - - -
Alloy 3 81.6 40.7 0.08 1.10 81.8 39.7 0.08 0.68 - - -
Alloy 4 81.5 40.5 0.08 1.28 82.7 39.6 0.08 0.59 81.6 40.9 0.17 0.:
These results are from process 4.
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Processes 3 and 4 generally gave the best results. The results for Processes 1
and 2 on
alloys 1 and 4 show slightly different results if the process is conducted in
the plant
(Process 2) rather than in the lab (Process 1) may have caused grain growth.
Table 15
shows that the double anneal process (Process 2) gives good bends when
simulated in
the lab.
Table 15 Additional results for Alloy 4
TS (KSI) YS KSl Eton % %IACS GW90 BW90
86.5 83.7 10.27 40.4 0.09 0.52
Plant processed alloys were subjected to stress relaxation testing at 150 C.
Results for the transverse direction only are shown below in Table 16. All
alloys except for
alloy 2 had at least 65% stress remaining after 1000h at 150 C.
Table 16 Stress Relaxation Data from the Plant Trial
Process 2 Process 3 or 4*
Results SR% 500h SR% 1000h SR% 500h SR% 1000h
Alloy 6 70.0 66.5
74.8 71.6
79.4 75.8
Alloy 5 72.5 68.7 76.2 72.1
Alloy 1 74.4 67.8 - -
Alloy 2 69.0 64.3 - -
Alloy 3 74.2 66.6 75.3 69.2
Alloy 4 71.4 66.5 73.8 68.2
22
