CN101874122A - Copper tin nickel phosphorus alloys with improved strength and formability - Google Patents
Copper tin nickel phosphorus alloys with improved strength and formability Download PDFInfo
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- CN101874122A CN101874122A CN200880113779A CN200880113779A CN101874122A CN 101874122 A CN101874122 A CN 101874122A CN 200880113779 A CN200880113779 A CN 200880113779A CN 200880113779 A CN200880113779 A CN 200880113779A CN 101874122 A CN101874122 A CN 101874122A
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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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 electrical conductivity with excellent formabiiity. 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 formabiiity of 11/11 minimum, and stress relaxation of 65% at 15O0C after 1000 hours. Processing can be modified to increase formabiiity 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
The cross reference of related application
The application requires the right of priority of No. the 60/979th, 064, the U.S. Provisional Patent Application submitted on October 10th, 2007, and it all openly incorporates this paper into.
Technical field
The present invention relates to copper alloy, be specifically related to copper-tin-nickel-phosphorus alloy that intensity and formability have been improved.
Background technology
To being used in electric connector, there is lasting demand in the high strength copper alloy with good formability and reasonable cost that particularly is used in the automobile electric connector.Electric current linker alloy in the low-cost Cu-Sn-Ni-P class lacks the combination of practical intensity (77KSI), middle specific conductivity (37%IACS), excellent formability and suitable stress relaxation (being 65% under 150 ℃) character.Formability herein crooked 90 ° to form bar is brought mensuration with it around mould of known radius by roller.The ratio of the minimum modulus radius that can form band and not rupture is divided by whole beam thickness.It is crooked that (bad mode (badway) is BW) with vertical (good way (good way) is measured on direction GW) parallel with rolling direction.Table 1 has shown present available Cu-Sn-Ni-P alloy:
Table 1: available linker alloy in the Cu-Sn-Ni-P class
C19025 is close to can realize required character, but lacks the intensity with suitable formability; C40820 has intensity and formability preferably, but does not have required specific conductivity.
Summary of the invention
Embodiments of the present invention combination or improved properties are provided copper-tin-nickel-phosphorus alloy, and the copper-tin-nickel-phosphorus alloy that provides yield strength and formability combination to improve especially.In a preferred implementation, described alloy comprises about Sn of 1%～about 2%; About 0.3%～1% Ni; About P of 0.05%～about 0.15%; At least a with among about Mg of 0.01%～about 0.20% and about 0.02%～about 0.4% the Fe, surplus is a copper.If do not need good stress relaxation in using, can add the low-cost surrogate of iron as Mg.More preferably described alloy comprises about Sn of 1.1%～about 1.8%, about Ni of 0.4%～about 0.9%, about P of 0.05%～about 0.14% and about Mg of 0.05～about 0.15.Fe can substitute some Mg.Most preferably described alloy comprises about Sn of 1.2%～about 1.5%; About Ni of 0.5%～about 0.7%; About P of 0.09%～about 0.13%; About Mg of 0.02%～about 0.06%, surplus is a copper.Preferred described alloy through be machined to the yield strength that has at least about 77KSI, at least about the specific conductivity of 37%IACS and the formability of 1.0/1.0 (90 ° of GW/BW).Described alloy also preferably has 65% stress relaxation under 150 ℃.
Sn strengthens alloy solid solution.Add Ni and Mg to form the throw out of phosphorus, have that Mg gains in strength and the advantage that do not reduce specific conductivity.Preferably the ratio (ratio of M/P) of metal (Ni+Mg) and P is controlled at 4～8.5 scope.If this ratio less than 4, can't obtain to strengthen; If this ratio is greater than 8.5, material can't be realized 40%IACS.
According to preferred implementation of the present invention, the processing of described alloy is by fusion and casting, about 850 ℃～about 1000 ℃ of hot rollings, be cold-rolled to the highest by about 75%, about 450 ℃～about 600 ℃ of annealing, it is about 60% to be cold-rolled to the highest reduction, subsequently 425 ℃～about 600 ℃ of annealing, is cold-rolled to about 50% before the annealing eventually at about 400 ℃～about 550 ℃.Before thermal stresses is eliminated processing, carry out final cold rolling reduction to reach desired thickness and physical strength.In another preferred embodiment, described processing comprises twice final annealing processing and saves upstream annealing that this has improved formability and intensity respectively.
Description of drawings
Fig. 1 is the Photomicrograph of embodiment 1 interalloy;
Fig. 2 is for concerning and illustrate the figure of the ratio of the preferred M/P that is used for the Cu-Sn-Ni-P-Mg alloy between the ratio that shows YS and M/P;
The ratio that Fig. 3 is used for the preferred M/P of Cu-Sn-Ni-P-Mg alloy for relation between the ratio that shows %IACS and M/P and explanation is 4～8.5 figure;
Fig. 4 A is the schema of the preferred implementation of alloy working method in accordance with the principles of the present invention;
Fig. 4 B is the schema of another preferred implementation of alloy working method in accordance with the principles of the present invention;
Fig. 4 C is the schema of another preferred implementation of alloy working method in accordance with the principles of the present invention;
Fig. 5 is the Photomicrograph of alloy 4 after the twice annealing, demonstrates the particle diameter between 6～7 μ m, and the some of them zone demonstrates the particle of not perfect recrystallization; And
Fig. 6 is the Photomicrograph of the alloy 4 of next comfortable band annealing back method 3, demonstrates the particle diameter of 4～5 μ m.
Embodiment
Embodiments of the present invention combination or improved properties are provided copper-tin-nickel-phosphorus alloy, and the copper-tin-nickel-phosphorus alloy that provides yield strength and formability combination to improve especially.In a preferred implementation, described alloy comprises about Sn of 1%～about 2%; About 0.3%～1% Ni; About P of 0.05%～about 0.15%; At least a with among about Mg of 0.01%～about 0.20% and about 0.02%～about 0.4% the Fe, surplus is a copper.If do not need good stress relaxation in using, can add the low-cost surrogate of iron as Mg.
More preferably, described alloy comprises about Sn of 1.2%～about 1.5%; About 0.5%～0.7% Ni; About P of 0.09%～about 0.13%; With about Mg of 0.02%～about 0.06%, surplus is a copper.Preferred described alloy through be machined to the yield strength that has at least about 77KSI, at least about the specific conductivity of 37%IACS and the formability of 1.0/1.0 (90 ° of GW/BW).Described alloy also preferably has 65% stress relaxation under 150 ℃.
Sn strengthens alloy solid solution.Add Ni and Mg to form the throw out of phosphorus, have that Mg gains in strength and the advantage that do not reduce specific conductivity.Preferably the ratio of M/P is controlled at 4～8.5 scope.If this ratio less than 4, can't obtain to strengthen; If this ratio is greater than 8.5, material can't be realized 40%IACS.
According to preferred implementation of the present invention, the processing of described alloy is by fusion and casting, 850 ℃～1000 ℃ hot rollings, be cold-rolled to the highest by about 75%, 450 ℃～600 ℃ annealing, cold rolling about 60%, subsequently 425 ℃～600 ℃ annealing, before 400 ℃～550 ℃ final annealings cold rolling about 50%.Before thermal stresses is eliminated processing, carry out final cold rolling reduction to reach desired thickness and physical strength.In another preferred embodiment, described processing comprises twice final annealing processing and saves upstream annealing that this has improved formability and intensity respectively.
Embodiment 1
To have in the table 2 a series of 10 pounds of experiments of listed composition and melt and cast swage with blank in silicon oxide crucibles, it is 4 " * 4 " * 1.75 after cast (gating) ".900 ℃ of following soaking after 2 hours, with their hot rollings 3 times to 1.1 " (1.6 "/1.35/1.1 "), 900 ℃ of following reheat 10 minutes, and by hot rolling " (0.9 "/0.7 "/0.5 " that further is reduced to 0.50 for 3 times), subsequently by water quenching.After finishing and milling, alloy is cold-rolled to 0.120 " and 570 ℃ of annealing 2 hours with the removal oxide on surface.With alloy cleaning and be cold-rolled to 0.048 ", and 525 ℃ of annealing 2 hours.Alloy is cold-rolled to 0.030 " and 500 ℃ of annealing 2 hours.Final cold rolling is 60%, to 0.012 ", and carried out stress relieving thermal treatment 2 hours at 250 ℃.
The alloy of table 2: embodiment 1 and character
| 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 |
*With herein, YS represents yield strength and represents with unit K SI at this table
Can determine that from the data of embodiment 2 Ni content is preferably at least 0.5, and best whole alloy has the ratio of 7～9 Ni/P.Because of there being the sulphur pollution that forms macrofiber shape inclusion (stringer) as shown in Figure 1, so all bendings are all relatively poor.
Embodiment 2
To have in the table 3 a series of 10 pounds of experiments of listed composition and melt and cast swage with blank in silicon oxide crucibles, it is 4 " * 4 " * 1.75 after cast ".900 ℃ of following soaking after 2 hours, with their hot rollings 3 times to 1.1 " (1.67 "/1.35/1.1 "), 900 ℃ of following reheat 10 minutes, and by hot rolling " (0.9 "/0.7 "/0.5 " that further is reduced to 0.50 for 3 times), subsequently by water quenching.After finishing and milling, alloy is cold-rolled to 0.120 " and 570 ℃ of annealing 2 hours with the removal oxide on surface.With alloy cleaning and be cold-rolled to 0.048 ", and 525 ℃ of annealing 2 hours.Alloy is cold-rolled to 0.024 " and 450 ℃ of annealing 8 hours.Final cold rolling is 50%, to 0.012 ", and carried out stress relieving thermal treatment 2 hours at 250 ℃.
The alloy of table 3: embodiment 2
Usually, except that alloy K293 and K294, its intensity is lower.These alloys contain than any other alloy Duos about 0.5% Sn, and higher Sn content is relevant with higher intensity.Very approaching with component, but it is opposite not contain alloy K282 and the K284 of Mg, and the intensity of K286, K287 and K288 has shown the benefit of Mg.It should be noted that specific conductivity (%IACS) does not reduce along with the increase of yield strength.By adding iron and add Mg in the K291 that does not contain Ni in the K289 that does not contain Ni, intensity increases.The specific conductivity of iron containing alloy is than the low about 4%IACS of the specific conductivity that contains the Mg alloy.These alloys are almost optimum balance; The ratio of the Mg/P of K289 is 1.81, and the ideal value near 1.2, and the ratio of the Fe/P of K291 is 4.00 is also near 3.6 ideal value.Iron is more effective toughener, but can cause lower specific conductivity.
Embodiment 3
To have in the table 4 a series of 10 pounds of experiments of listed composition and melt and cast swage with blank in silicon oxide crucibles, it is 4 " * 4 " * 1.75 after cast ".900 ℃ of following soaking after 2 hours, with their hot rollings 3 times to 1.1 " (1.6 "/1.35/1.1 "), 900 ℃ of following reheat 10 minutes, and by hot rolling " (0.9 "/0.7 "/0.5 " that further is reduced to 0.50 for 3 times), subsequently by water quenching.After finishing and milling, alloy is cold-rolled to 0.120 " and 570 ℃ of annealing 2 hours with the removal oxide on surface.With alloy cleaning and be cold-rolled to 0.048 ", and 525 ℃ of annealing 2 hours.Alloy is cold-rolled to 0.024 ", only be used for 450 ℃ of single annealing conditions annealing 4 hours down, and constituting 450 ℃ of twice annealing condition annealing 4 hours and 375 ℃ of annealing 4 hours in addition down down.For two kinds of conditions, final cold rolling is 50%, to 0.012 ", and carried out stress relieving thermal treatment 2 hours at 250 ℃.
Table 4: the alloy that comprises the embodiment 3 of two kinds of annealing conditions
Higher Sn content significantly improves strength level, but specific conductivity is lower.Compare alloy K320 and K319; YS differs 7KSI and specific conductivity differs 3%IACS.Although this intensity effect is lower to those alloys without any other additive, this trend still is applicable to those alloys of iron content (K312 and K313) and contains those alloys of magnesium (K314 and K315).Compare with K310, zinc K311 does not have global advantage; Intensity increases but specific conductivity is lower.Twice annealing demonstrates formability increases (that is, attainable 90 ° of bending radius reduce).Also notice the slight increase on the specific conductivity.
Embodiment 4
To have in the table 4 a series of 10 pounds of experiments of listed composition and melt and cast swage with blank in silicon oxide crucibles, it is 4 " * 4 " * 1.75 after cast ".900 ℃ of following soaking after 2 hours, with their hot rollings 3 times to 1.1 " (1.6 "/1.35/1.1 "), 900 ℃ of following reheat 10 minutes, and by hot rolling " (0.9 "/0.7 "/0.5 " that further is reduced to 0.50 for 3 times), subsequently by water quenching.After finishing and milling, alloy is cold-rolled to 0.120 " and 570 ℃ of annealing 2 hours with the removal oxide on surface.With alloy cleaning and be cold-rolled to 0.048 ", and 525 ℃ of annealing 2 hours.Alloy is cold-rolled to 0.024 ", annealed 4 hours in addition 450 ℃ of annealing 4 hours and at 375 ℃.Final cold rolling is 50%, to 0.012 ", and carried out stress relieving thermal treatment 2 hours at 250 ℃.
The data of table 5: embodiment 4
| Alloy | ??YS | ??EL％ | ??IACS％ | ??90GW | ??90BW | ??SN | ??NI | ??P | ??FE | ??MG | ??M/P |
| ??K335 | ??71.5 | ??11.41 | ??42.4 | ??0.26 | ??0.26 | ??1.13 | ??0.52 | ??0.086 | ??0 | ??0 | ??6.05 |
| ??K336 | ??71.2 | ??9.93 | ??41.4 | ??0.34 | ??0.17 | ??1.28 | ??0.69 | ??0.053 | ??0 | ??0 | ??13.02 |
| Alloy | ??YS | ??EL％ | ??IACS％ | ??90GW | ??90BW | ??SN | ??NI | ??P | ??FE | ??MG | ??M/P |
| ??K337 | ??72.5 | ??12.08 | ??41.7 | ??0.08 | ??0.17 | ??1.46 | ??0.51 | ??0.075 | ??0 | ??0 | ??6.80 |
| ??K338 | ??76.3 | ??12.78 | ??38.2 | ??0.08 | ??0.25 | ??1.38 | ??0.53 | ??0.099 | ??0.37 | ??0 | ??9.09 |
| ??K339 | ??78.9 | ??11.99 | ??36.6 | ??0.08 | ??0.67 | ??1.7 | ??0.53 | ??0.105 | ??0.33 | ??0 | ??8.19 |
| ??K340 | ??73.6 | ??12.66 | ??41.4 | ??0.17 | ??0.50 | ??1.45 | ??0.52 | ??0.079 | ??0 | ??0 | ??6.58 |
| ??K341 | ??73.5 | ??11.79 | ??39.1 | ??0.17 | ??0.34 | ??1.47 | ??0.69 | ??0.064 | ??0 | ??0 | ??10.78 |
| ??K342 | ??73.5 | ??11.76 | ??41.7 | ??0.25 | ??0.16 | ??1.43 | ??0.53 | ??0.067 | ??0 | ??0 | ??7.91 |
| ??K343 | ??75.2 | ??12.77 | ??38.4 | ??0.08 | ??0.33 | ??1.71 | ??0.53 | ??0.08 | ??0 | ??0 | ??6.63 |
| ??K344 | ??71.9 | ??10.51 | ??38 | ??0.67 | ??0.67 | ??1.67 | ??0.52 | ??0.033 | ??0 | ??0 | ??15.76 |
| ??K345 | ??74.8 | ??11.84 | ??38.6 | ??0.08 | ??0.17 | ??1.61 | ??0.69 | ??0.076 | ??0 | ??0 | ??9.08 |
| ??K346 | ??74.8 | ??10.02 | ??38.4 | ??0.08 | ??0.08 | ??1.35 | ??0.32 | ??0.105 | ??0.4 | ??0 | ??6.90 |
| ??K347 | ??76.5 | ??10.58 | ??41.4 | ??0.08 | ??0.17 | ??1.38 | ??0.3 | ??0.143 | ??0.23 | ??0 | ??3.70 |
| ??K348 | ??75.4 | ??12.48 | ??32.8 | ??2.00 | ??3.00 | ??1.71 | ??0.32 | ??0.139 | ??0 | ??0 | ??2.40 |
| ??K349 | ??70.5 | ??12.53 | ??41.5 | ??0.50 | ??0.50 | ??1.35 | ??0.53 | ??0.035 | ??0 | ??0 | ??15.14 |
| ??K350 | ??76.3 | ??13.37 | ??38.1 | ??0.17 | ??0.25 | ??1.62 | ??0.7 | ??0.081 | ??0 | ??0.031 | ??9.00 |
| ??K351 | ??76.3 | ??10.72 | ??40.6 | ??0.08 | ??0.33 | ??1.35 | ??0.69 | ??0.092 | ??0 | ??0.049 | ??8.00 |
| ??K352 | ??75.8 | ??12.55 | ??41 | ??0.17 | ??0.17 | ??1.37 | ??0.54 | ??0.129 | ??0 | ??0.021 | ??4.30 |
| ??K355 | ??78.7 | ??13.83 | ??37.1 | ??0.25 | ??0.50 | ??1.74 | ??0.32 | ??0.145 | ??0.21 | ??0 | ??3.66 |
| ??K356 | ??75.6 | ??11.99 | ??41.5 | ??0.67 | ??0.67 | ??1.42 | ??0.54 | ??0.09 | ??0 | ??0.041 | ??7.00 |
| ??K361 | ??78.7 | ??15.11 | ??34.2 | ??0.34 | ??0.50 | ??1.7 | ??0.33 | ??0.151 | ??0.043 | ??0 | ??2.47 |
There are 13 kinds of alloys to have 75KSI or higher yield strength in 22 kinds of alloys of this group.6 kinds of iron content (K338, K339, K345, K346, K355 and K361) are 40%IACS although K338, does not wherein have a kind of specific conductivity near 38%IACS.4 kinds contain Mg (K350, K351, K352 and K356), and this wherein has 3 kinds greater than 40%IACS.Notice that metal that the K350 of no show 40%IACS has and phosphorus ratio are 9, greater than recommended 8.5.In yield strength is in 75KSI or the bigger alloy, have 3 kinds neither iron content do not contain Mg (K343, K345 and K348) yet, but these alloys all do not have the specific conductivity of 40%IACS.
Embodiment 5
The all data that contains the Mg alloy and do not contain the Mg alloy is incorporated in table 6 and 7.These data come from embodiment 2 (through twice annealing, and being included in table 3 alloy in table 6 and 7), embodiment 3 (table 4) and embodiment 4 (table 5), and comprise the data that come from embodiment 3.The method that is used for whole alloys with 450 ℃ following 4 hours (or 8 hours; See note) identical with method used in 375 ℃ of final twice annealing of following 4 hours.
Table 6: the integrated data of coming whole embodiment (all twice annealing) of self-contained Mg
Table 7: from the integrated data of whole embodiment of no Mg (all twice annealing)
*Alloy K319 and K320 and C19020 and C19025 are similar, but P is less.
The alloy that highlights with light gray have 450 ℃ following 8 hours with 375 ℃ of slight different final twice annealing of following 4 hours.
On the whole, the YS that contains Mg in table 6 is higher than the YS that does not contain Mg in the table 7.Only have the alloy that does not contain on a small quantity Mg to reach minimum YS:K293, K294, K310, K326, K343, K345 and the K348 of 75KSI, corresponding specific conductivity is respectively 42.2,38.5,38.5,38.5,38.4,38.6 and 32.8%IACS.It should be noted that except that K293 do not have alloy to reach 40%IACS in these alloys.Alloy K293, K294 and K326 have YS and the specific conductivity character that approaches C19025, but have crooked preferably.On the contrary, except K289 and K290 (its ratio that does not contain Ni and M/P is less than 4), the Mg alloy all has the YS that is at least 75KSI in the table 6.Except that having M/P is that the ratio of 7.66 K318 (38.7%IACS) and M/P is 9.02 the K350 (38.1%IACS), and all the specific conductivity of alloys is 40%IACS or greater than 40%IACS.Along with the increase of metal and phosphorus ratio, the combination of specific conductivity reduction and required character becomes and more is difficult to realize.When the ratio of using suitable working method and maintenance M/P was 4～8.5, the adding of Mg can realize that yield strength is the combination of 40%IACS at least greater than 75KSI and specific conductivity.Fig. 2 and 3 has illustrated the relation between this ratio and YS and the %IACS respectively.Vertical line among Fig. 2 shows that the ratio of preferred L/P is 4～8.5.
Embodiment 7
To have in the table 8 a series of 10 pounds of experiments of listed composition and melt and cast swage with blank in silicon oxide crucibles, it is 4 " * 4 " * 1.75 after cast ".900 ℃ of following soaking after 2 hours, with their hot rollings 3 times to 1.1 " (1.6 "/1.35/1.1 "), 900 ℃ of following reheat 10 minutes, and by hot rolling " (0.9 "/0.7 "/0.5 " that further is reduced to 0.50 for 3 times), subsequently by water quenching.After finishing and milling, alloy is cold-rolled to 0.080 " and 550 ℃ of annealing 2 hours with the removal oxide on surface.With alloy cleaning and be cold-rolled to 0.036 ", 450 ℃ of annealing 4 hours and 375 ℃ of annealing 4 hours in addition.Final cold rolling is 60%, to 0.012 ", and carried out stress relieving thermal treatment 2 hours at 250 ℃.
The data of table 8: embodiment 7
| Alloy | ??TS | ??YS | ??EL％ | ??IACS％ | ??90GW | ??90BW | ??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 |
The cold process modification that increases the intensity of whole alloys.Yet the ratio of M/P is unique improvement YS and the alloy that keeps or improve specific conductivity less than 9 the Mg alloy (K352) that contains.
Embodiment 8
To have in the table 3 a series of 10 pounds of experiments of listed composition and melt and cast swage with blank in silica crucible, it is 4 " * 4 " * 1.75 after cast ".900 ℃ of following soaking after 2 hours, with their hot rollings 3 times to 1.1 " (1.6 "/1.35/1.1 "), 900 ℃ of following reheat 10 minutes, and by hot rolling " (0.9 "/0.7 "/0.5 " that further is reduced to 0.50 for 3 times), subsequently by water quenching.After finishing and milling, alloy is cold-rolled to 0.120 " and 570 ℃ of annealing 2 hours with the removal oxide on surface.With alloy cleaning and be cold-rolled to 0.048 ", and 525 ℃ of annealing 2 hours.Alloy is cold-rolled to 0.024 " and 450 ℃ of minimum annealing 4 hours.Final cold rolling is 50%, to 0.012 ", and carried out stress relieving thermal treatment 2 hours at 250 ℃.Make sample in the stress relaxation test in 1000 hours of 150 ℃ of experience.The result provides in following table 9.
The data of table 9: embodiment 8
| Alloy | Form | Residual stress % |
| ??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 |
Ferruginous alloy K291 and K312 do not keep 60% initial stress.Although there is Ni among the K312, result between the two is similar.The K314 that contains Ni and Mg combination keeps the initial stress greater than 65%.
Embodiment 9
Use described tabulation to process one group of Mg alloy and do not contain the alloy of Mg.Table 10 and 11 has been summed up its result.Two combination gold have realized that all yield strength is greater than 80KSI.Contain the Mg alloy all above the target specific conductivity of 38%IACS, and except that K412, the alloy that does not contain Mg does not surpass all.In addition, it is better generally to contain the formability of Mg alloy.
Table 10: contain Mg alloy result's summary
| Alloy | ??YS | ??EL％ | ??％IACS | ??90GW | ??90BW | ??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 | ??1.00 | ??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 |
| Alloy | ??YS | ??EL％ | ??％IACS | ??90GW | ??90BW | ??Sn | ??Ni | ??P | ??Mg | Metal/P |
| ??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 | ??9.86 |
| ??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
Method describes in detail: HRP+CR to 0.060 specification (gage)+500 ℃/8 hours+CR, 50% to 0.030 specification+450 ℃/4 hours+375 ℃/4 hours+CR, 60% to 0.012 specification+250 ℃/2 hours
Table 11: do not contain Mg alloy result's summary
| 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
Method describes in detail: HRP+CR to 0.060 specification+475 ℃/16 hours+CR, 50% to 0.030 specification+450 ℃/4 hours+375 ℃/4 hours+CR, 60% to 0.012 specification+250 ℃/2 hours
6 kinds of alloys of his-and-hers watches 12 listed normal compositions carry out batch production processing.These methods describe in detail in table 13, and wherein method 1 is for being used for the laboratory method of comparison, and method 2,3 and 4 is the batch production method.
Table 12: the chemical constitution of institute of factory process bars
| Alloy | ??Sn | ??Ni | ??P | ??Mg |
| ??1 | ??1.64 | ??0.88 | ??0.074 | ??0 |
| ??2 | ??1.7 | ??0.65 | ??0.1 | ??0 |
| Alloy | ??Sn | ??Ni | ??P | ??Mg |
| ??3 | ??1.39 | ??0.65 | ??0.1 | ??0.035 |
| ??4 | ??1.42 | ??0.68 | ??0.11 | ??0.038 |
| ??5 | ??1.66 | ??1 | ??0.1 | ??0 |
| ??6 | ??0.91 | ??0.98 | ??0.056 | ??0 |
Given chemical constitution is a cast rod chemical constitution by analysis in the table 12.Alloy 6 and exists with comparative example in the CDA of C19025 scope.All alloy is processed in the same way: they are all 900 ℃ of following hot rollings, and cold grinding also is cold-rolled to 0.125 or 0.100 specification subsequently.
The explanation of table 13: embodiment 10 methods
| Method 1 | Method 2 | Method 3 | Method 4 |
| ??HR | ??HR+CR→0.100 | ?HR+CR→0.125 | ?HR+CR→0.125 |
| ??CR→0.060 | ??CR→0.060 | ||
| Annealed 500 ℃/8 hours | 500 ℃ of annealing are with abundant recrystallize | 520 ℃ of annealing are with abundant recrystallize | 520 ℃ of annealing are with abundant recrystallize |
| ??CR→0.030 | ??CR→0.0295 | ?CR→0.0295 | ?CR→0.0513 |
| 450 ℃/4 hours+375 ℃/4 hours | 450 ℃/6 hours+25 ℃/hour slowly cooled to 375 ℃/5.5 hours | ?570℃ | ?580℃ |
| ??CR→0.012 | ??CR→0.0118 | ?CR→0.0118 | ?CR→0.0118 |
| 250 ℃/2 hours | ??400℃ | ?400℃ | ?400℃ |
Gained character is presented in the table 14 when final specification.The alloy 6 of using method 3 and 4 processing has the desirable character of this alloy, compares with method 3, and the alloy 6 of method 4 processing has higher yield strength and relatively poor bending.With method 3 metallographic phase ratio, when adding man-hour according to method 2, alloy 5 has lower yield strength (YS) and relatively poor bad mode bending.The alloy 3 of method 2 and method 3 processing has suitable yield strength and specific conductivity, but the metal of method 3 processing has bad preferably mode bending.
Table 14: with the metallographic phase ratio of laboratory processing, from the result of plant experiment
*These results come from method 4.
Method 3 and 4 provides best result generally.If method is in factory's (method 2) but not carry out in laboratory (method 1), on alloy 1 and 4, the result that method 1 and 2 result demonstrate Light Difference can cause grain growing.Table 15 shows that it provides good bending when simulation twice annealing method (method 2) in the laboratory.
Table 15: other result of alloy 4
The metal that makes factory process is in the test of 150 ℃ of experience stress relaxation.
Horizontal result only is presented in the following table 16.Except that alloy 2, all alloy still has at least 65% residual stress after 1000 hours in experience under 150 ℃.
Table 16: from the stress relaxation data of plant experiment
Claims (25)
1. a copper base alloy comprises about Sn of 1%～about 2%; About Ni of 0.3%～about 1%; About P of 0.05%～about 0.15%; Be up at least a among about 0.20% Mg and about 0.1%～about 0.4% the Fe, surplus is a copper.
2. copper base alloy as claimed in claim 1 contains Mg and does not contain Fe.
3. copper base alloy as claimed in claim 1 contains Fe and does not contain Mg.
4. copper base alloy as claimed in claim 1 contains Mg and Fe.
5. copper base alloy as claimed in claim 1 contains and is up to about 0.06% Mg.
6. copper base alloy as claimed in claim 1 to have the yield strength at least about 77KSI, keeps the crooked formability (90 ° of GW/BW) of 1.0/1.0 through processing simultaneously.
7. copper base alloy as claimed in claim 6, wherein said alloy is through processing to have the specific conductivity at least about 37%IACS.
8. copper base alloy as claimed in claim 6, wherein said alloy is through processing to have the specific conductivity at least about 40%IACS.
9. copper base alloy as claimed in claim 1, the ratio of wherein said Ni: P is less than about 9.
10. copper base alloy as claimed in claim 1, the ratio of wherein said (Ni+Mg): P are about 4～about 8.5.
11. copper base alloy as claimed in claim 1, wherein said Sn be about 1.2%～about 1.5%, described Ni is about 0.5%～0.7%, and described P is about 0.09%～about 0.13%.
12. copper base alloy as claimed in claim 11, the ratio of wherein said Ni: P is less than about 9.
13. copper base alloy as claimed in claim 11, the ratio of wherein said (Ni+Mg): P are about 4～about 8.5.
14. copper base alloy as claimed in claim 11 to have the yield strength at least about 77KSI, keeps the crooked formability (90 ° of GW/BW) of 1.0/1.0 through processing simultaneously.
15. copper base alloy as claimed in claim 14, wherein said alloy is through processing to have the specific conductivity at least about 37%IACS.
16. copper base alloy as claimed in claim 14, wherein said alloy is through processing to have the specific conductivity at least about 40%IACS.
17. a copper base alloy comprises about Sn of 1.2%～about 1.5%; About Ni of 0.5%～about 0.7%; About P of 0.09%～about 0.13%; And be up at least a among about 0.20% Mg and about 0.1%～about 0.4% the Fe, surplus is a copper, described alloy through processing to have at least about the yield strength of 77KSI with at least about the specific conductivity of 37%IACS.
18. copper base alloy as claimed in claim 17, wherein said alloy is through processing to have the specific conductivity at least about 40%IACS.
19. copper base alloy as claimed in claim 17 is through the crooked formability (90 ° GW/BW) of processing to have 1.0/1.0.
20. copper base alloy as claimed in claim 11, the ratio of wherein said (Ni+Mg): P are about 4～about 8.5.
21. a method of processing copper base alloy, described copper base alloy comprise about Sn of 1%～about 2%; About Ni of 0.03%～about 1%; About P of 0.05%～about 0.15%; And be up at least a among about 0.20% Mg and about 0.1%～about 0.4% the Fe, described method comprises:
Cast described alloy;
At about 850～about 1000 ℃ of described alloys of following hot rolling;
Make described alloy experience once cold rolling and annealing at least, so that the abundant recrystallize of described alloy;
Cold rolling described alloy is to desired thickness and physical strength; With
Described alloy experience thermal stresses is eliminated handled, be at least about the alloy that 77KSI and specific conductivity are at least about 37%IACS so that yield strength to be provided.
22. method as claimed in claim 21 wherein has three cold rolling and annealing at least.
23. method as claimed in claim 22, wherein said have at least three cold rolling and annealing to comprise:
First is cold rolling, about 75% to the highest reduction, subsequently about 450 ℃～about 600 ℃ of annealing 1～48 hour;
Second is cold rolling, about 60% to the highest reduction, subsequently about 425 ℃～about 600 ℃ of annealing 1～48 hour; With
The 3rd is cold rolling, about 50% to the highest reduction, subsequently about 400 ℃～about 550 ℃ of annealing 1～48 hour.
24. method as claimed in claim 22, the once annealing in the wherein said annealing comprises the branch step annealing.
That 25. method as claimed in claim 24, wherein said minute step annealing are included in is about 400～about 500 ℃ first annealing and subsequently in about 300～second about 400 ℃ annealing.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US97906407P | 2007-10-10 | 2007-10-10 | |
| US60/979,064 | 2007-10-10 | ||
| US12/249,530 US20090098011A1 (en) | 2007-10-10 | 2008-10-10 | Copper Tin Nickel Phosphorus Alloys With Improved Strength and Formability and Method of Making Same |
| US12/249,530 | 2008-10-10 | ||
| PCT/US2008/079573 WO2009049201A1 (en) | 2007-10-10 | 2008-10-10 | Copper tin nickel phosphorus alloys with improved strength and formability |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101874122A true CN101874122A (en) | 2010-10-27 |
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|---|---|---|---|
| CN200880113779A Pending CN101874122A (en) | 2007-10-10 | 2008-10-10 | Copper tin nickel phosphorus alloys with improved strength and formability |
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|---|---|
| US (1) | US20090098011A1 (en) |
| EP (1) | EP2215278A4 (en) |
| JP (1) | JP5752937B2 (en) |
| CN (1) | CN101874122A (en) |
| CA (1) | CA2702358A1 (en) |
| MX (1) | MX2010003995A (en) |
| TW (1) | TW200934882A (en) |
| WO (1) | WO2009049201A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110462091A (en) * | 2017-02-04 | 2019-11-15 | 美题隆公司 | The method for producing adonic |
| CN113981265A (en) * | 2021-09-07 | 2022-01-28 | 铜陵有色金属集团股份有限公司金威铜业分公司 | Copper alloy having excellent hot rolling properties and method for producing same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US8821655B1 (en) | 2010-12-02 | 2014-09-02 | Fisk Alloy Inc. | High strength, high conductivity copper alloys and electrical conductors made therefrom |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4908275A (en) * | 1987-03-04 | 1990-03-13 | Nippon Mining Co., Ltd. | Film carrier and method of manufacturing same |
| JPH0616522B2 (en) * | 1987-03-04 | 1994-03-02 | 日本鉱業株式会社 | Copper alloy foil for tape carrier |
| US5322575A (en) * | 1991-01-17 | 1994-06-21 | Dowa Mining Co., Ltd. | Process for production of copper base alloys and terminals using the same |
| US6254702B1 (en) * | 1997-02-18 | 2001-07-03 | Dowa Mining Co., Ltd. | Copper base alloys and terminals using the same |
| US7182823B2 (en) * | 2002-07-05 | 2007-02-27 | Olin Corporation | Copper alloy containing cobalt, nickel and silicon |
| JP4660735B2 (en) * | 2004-07-01 | 2011-03-30 | Ｄｏｗａメタルテック株式会社 | Method for producing copper-based alloy sheet |
| JP4984108B2 (en) * | 2005-09-30 | 2012-07-25 | Ｄｏｗａメタルテック株式会社 | Cu-Ni-Sn-P based copper alloy with good press punchability and method for producing the same |
| JP4810703B2 (en) * | 2005-09-30 | 2011-11-09 | Ｄｏｗａメタルテック株式会社 | Copper alloy production method |
| JP4680765B2 (en) * | 2005-12-22 | 2011-05-11 | 株式会社神戸製鋼所 | Copper alloy with excellent stress relaxation resistance |
| JP5075438B2 (en) * | 2007-03-20 | 2012-11-21 | Ｄｏｗａメタルテック株式会社 | Cu-Ni-Sn-P copper alloy sheet and method for producing the same |
-
2008
- 2008-10-10 JP JP2010529100A patent/JP5752937B2/en active Active
- 2008-10-10 CN CN200880113779A patent/CN101874122A/en active Pending
- 2008-10-10 US US12/249,530 patent/US20090098011A1/en not_active Abandoned
- 2008-10-10 EP EP08837615.7A patent/EP2215278A4/en not_active Withdrawn
- 2008-10-10 MX MX2010003995A patent/MX2010003995A/en unknown
- 2008-10-10 CA CA2702358A patent/CA2702358A1/en not_active Abandoned
- 2008-10-10 WO PCT/US2008/079573 patent/WO2009049201A1/en active Application Filing
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110462091A (en) * | 2017-02-04 | 2019-11-15 | 美题隆公司 | The method for producing adonic |
| CN110462091B (en) * | 2017-02-04 | 2022-06-14 | 美题隆公司 | Method for producing copper-nickel-tin alloy |
| CN114959230A (en) * | 2017-02-04 | 2022-08-30 | 美题隆公司 | Copper-nickel-tin alloy strip or plate and preparation method thereof |
| CN114959230B (en) * | 2017-02-04 | 2024-08-16 | 美题隆公司 | Copper nickel tin alloy strip or plate and preparation method thereof |
| CN113981265A (en) * | 2021-09-07 | 2022-01-28 | 铜陵有色金属集团股份有限公司金威铜业分公司 | Copper alloy having excellent hot rolling properties and method for producing same |
Also Published As
| Publication number | Publication date |
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| EP2215278A4 (en) | 2015-09-02 |
| MX2010003995A (en) | 2010-09-30 |
| US20090098011A1 (en) | 2009-04-16 |
| EP2215278A1 (en) | 2010-08-11 |
| JP2011500963A (en) | 2011-01-06 |
| WO2009049201A1 (en) | 2009-04-16 |
| TW200934882A (en) | 2009-08-16 |
| JP5752937B2 (en) | 2015-07-22 |
| CA2702358A1 (en) | 2009-04-16 |
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