CA2702358A1 - Copper tin nickel phosphorus alloys with improved strength and formability - Google Patents

Abstract

A new copper-based alloy is described along with a processing method to make a strip that can be used for various automotive interconnects.
The alloy process combination yields a material with high strength and electncal conductivity with excellent formability.
The combination of properties result from a Cu-Sn-Ni-P alloy with optional Mg additions and thermal-mechanical processing to make an alloy with a conductivity of 40%iACS, yield strength of 80 KSI, bend formability of 11/11 minimum, and stress relaxation of 65% at 150°C after 1000 hours. Processing can be modified to increase formability at the expense of yield strength. Improvements to conductivity come from changes in chemistry as well as processing. The new chemistry-process optimization results in a low cost alloy of Cu-Sn-Ni-P-Mg.

Description

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:

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 @

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 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 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.

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 %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 850-1000 -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 *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.

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 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.

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.

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.

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 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.

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_ 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

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

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 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.

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:

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.

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 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 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.

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.

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

Claims (25)

1. A copper base alloy comprising 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 up to about 0.20% Mg and between about 0.1 and about 0.4%
Fe, the balance being copper.

2. The copper base alloy according to claim 1 containing Mg but no Fe.

3. The copper base alloy according to claim 1 containing Fe but no Mg.

4. The copper base alloy according to claim 1 containing both Mg and Fe.

5. The copper base alloy according to claim 1 containing up to about 0.06% Mg.

6. The copper base alloy according to claim 1 processed to have a yield strength of at least about 77 ksi, while maintaining bend formability (90° GW/BW) of 1.0/1Ø

7. The copper base alloy according to claim 6 wherein the alloy is processes to have a conductivity of at least about 37% IACS.

8. The copper base alloy according to claim 6 wherein the alloy is processed to have a conductivity of at least about 40% IACS

9. The copper base alloy according to claim 1 wherein the Ni:P ratio is less than about 9.

10. The copper alloy according to claim 1 wherein the (Ni+Mg):P ratio is between about 4 and about 8.5.

11. The copper base alloy according to claim 1 wherein the Sn is between about 1.2% and about 1.5%, the Ni is between about 0.5% and 0.7%, and the P
is between about 0.09% and about 0.13%.

12. The copper base alloy according to claim 11 wherein the Ni:P ratio is less than about 9.

13. The copper alloy according to claim 11 wherein the (Ni+Mg):P ratio is between about 4 and about 8.5.

14. The copper base alloy according to claim 11 processed to have a yield strength of at least about 77 ksi, while maintaining bend formability (90 GW/BW) of 1.0/1Ø

15. The copper base alloy according to claim 14 wherein the alloy is process to have a conductivity of at least about 37% IACS.

16. The copper base alloy according to claim 14 wherein the alloy is process to have a conductivity of at least about 40% IACS.

17. A copper base alloy comprising 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 at least one of up to about 0.20% Mg and between about 0.1 and about 0.4% Fe, the balance being copper, the alloy processed to have a yield strength of at least about 77 ksi, and an electrical conductivity of at least about 37% EACS.

18. The copper base alloy according to claim 17 wherein the alloy is processed to have a conductivity of at least about 40% IACS.

19. The copper base alloy according to claim 17 processed to have a bend formability (90° GW/BW) of 1.0/1Ø

20. The copper alloy according to claim 11 wherein the (Ni+Mg):P ratio is between about 4 and about 8.5.

21. A method of processing a copper base alloy comprising between about 1% and about 2% Sn; between about 0.03% and about 1%Ni; between about 0.05% and about 0.15% P, and at least one of up to about 0.20% Mg and between about 0.1 and about 0.4% Fe, the method comprising:

casting the alloy;

hot rolling the alloy at about 850 to about 1000°C;

subjecting the alloy to at least one cold rolling and annealing to substantially recrystalize the alloy;

cold rolling the alloy to the desired thickness and mechanical strength; and subjecting the alloy to a thermal stress relief treatment, to provide an alloy with a yield strength of at least about 77 ksi and an electrical conductivity of at least about 37% IACS.

22. The method according to claim 21 wherein there are at least three cold rollings and annealings.

23. The method according to claim 22 wherein the at least three cold rollings and annealings comprise:

a first cold rolling up to about a 75% reduction followed by annealing between about 450 and about 600°C for 1 to 48 hours;

a second cold rolling up to about a 60% reduction followed by annealing at about 425 and about 600°C for 1 to 48 hours; and a third cold rolling up to about a 50% reduction followed by an annealing at between about 400 and about 550°C for 1 to 48 hours.

24. The method according to claim 22 wherein one of the annealings comprises a step anneal.

25. The method according to claim 24 wherein the step anneal comprises a first anneal at between about 400 and about 500 °C followed by a second anneal at between about 300 and about 400 °C.