WO1999005331A1 - Alliage de cuivre au magnesium - Google Patents
Alliage de cuivre au magnesium Download PDFInfo
- Publication number
- WO1999005331A1 WO1999005331A1 PCT/US1998/013925 US9813925W WO9905331A1 WO 1999005331 A1 WO1999005331 A1 WO 1999005331A1 US 9813925 W US9813925 W US 9813925W WO 9905331 A1 WO9905331 A1 WO 9905331A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- copper alloy
- weight percent
- magnesium
- copper
- phosphorous
- Prior art date
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- 239000011777 magnesium Substances 0.000 title claims abstract description 87
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 85
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 80
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 79
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 118
- 229910052742 iron Inorganic materials 0.000 claims abstract description 66
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000956 alloy Substances 0.000 claims abstract description 54
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 53
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052802 copper Inorganic materials 0.000 claims abstract description 31
- 239000010949 copper Substances 0.000 claims abstract description 31
- 239000006104 solid solution Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 21
- 238000005096 rolling process Methods 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims 1
- 238000007792 addition Methods 0.000 abstract description 11
- 230000035882 stress Effects 0.000 description 47
- 239000002245 particle Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 230000008901 benefit Effects 0.000 description 7
- 239000005953 Magnesium phosphide Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000005275 alloying Methods 0.000 description 4
- 238000005098 hot rolling Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006355 external stress Effects 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 229910001315 Tool steel Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000001814 effect on stress Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
Definitions
- This invention relates to a copper alloy having high strength, high electrical conductivity and a resistance to stress relaxation at elevated temperatures. More particularly, the resistance to stress relaxation is enhanced by the presence of magnesium in solution with the copper. Elemental copper has a very high electrical conductivity and relatively low strength and poor resistance to stress relaxation. Stress relaxation is an important consideration when selecting a copper alloy for an application where the product will be subjected to external stresses, such as when used for a spring or an electrical connector component. Stress relaxation is a phenomenon that occurs when an external stress is applied to a piece of metal. The metal reacts by developing an equal and opposite internal stress. If the metal is restrained in the strained position, the internal stress decreases as a function of time.
- a sheet of copper alloy may be deformed into a hollow, generally cylindrical shape for use as a socket. Metal adjacent to an open end of the cylinder is externally stressed, such as by bending, to develop an opposing internal stress effective to cause the ends of the copper strip to bias inward and tightly contact a mating plug.
- Copper alloy C 19700 One copper alloy used to manufacture electrical connector components is designated by the Copper Development Association (CD A, Greenwich, CT) as copper alloy C 19700.
- Copper alloy C 19700 has the nominal composition, by weight, of 0.3%-1.2% iron, 0.1%-0.4% phosphorous, 0.01%-0.2% magnesium and the balance copper and unavoidable impurities.
- Copper alloy C 19700 has a resistance to stress relaxation that is marginal for many applications at exposure temperatures of 105°C or higher, particularly in the transverse orientation and for stronger tempers. It has been determined that after 3000 hours at an exposure temperature of 105°C, a copper alloy C 19700 connector in the hard temper, typically has about 64% stress remaining in the longitudinal direction and 56% stress remaining in the transverse direction.
- the resistance to stress relaxation can be improved by a relief anneal.
- the copper alloy sheet After the copper alloy sheet is rolled to final gage, it may be relief annealed for a hard temper by bell annealing at a strip temperature of from 200°C to 400°C for from 30 seconds to 4 hours. Strip annealing at corresponding higher temperatures and shorter exposure times is also useful.
- a connector formed from copper alloy C 19700 in the hard/relief anneal temper typically has a longitudinal value of 72% stress remaining and a transverse value of 65% stress remaining after the same exposure to 105°C for 3000 hours.
- a sheet 10 of a desired copper alloy is reduced in thickness by passing through the rolls 12 of a rolling mill.
- the copper alloy sheet 10 then has a longitudinal axis 14 along the rolling direction that is perpendicular to an axis 16 about which the rolls 12 rotate.
- the transverse axis 18 of the copper alloy sheet 10 is perpendicular to the longitudinal axis 14.
- Spring contacts formed from the copper alloy sheet and oriented parallel to the rolling direction are referred to as having a longitudinal (or good-way) orientation while spring contacts having an orientation transverse to the rolling direction are referred to as having a transverse (or bad-way) orientation.
- United States patents that disclose a copper alloy containing iron, phosphorous and magnesium include United States Patent No. 4,305,762 to Caron et al. and United States Patent No. 4,605,532 to Knorr et al.
- the Caron et al. patent discloses a copper alloy containing 0.04%- 0.20% of magnesium, phosphorous and iron.
- the Knorr et al. patent discloses a copper alloy containing 0.01%-0.20% magnesium, 0.1%-0.4% phosphorous, 0.3%-1.6% iron and the balance copper.
- Published Japanese patent application No. JP 58-199835 by Sumitomo Electric discloses a copper alloy that contains 0.03%-0.3% magnesium, 0.03%-0.3% iron, 0.1%-0.3% phosphorous and the balance copper.
- copper is alloyed with various other elements, and combinations of elements, to increase strength.
- the alloying additions frequently impact other alloy properties. If the alloying additions are in solid solution with the copper, conductivity is frequently reduced. If the alloying additions result in large, hard, second phase particles, the surface finish of the copper alloy after cold rolling to sheet form may be marred by voids around these second phase particles. These voids can adversely affect the quality of an electrolytically deposited coating on the alloy. It is, therefore, an objective to maximize the strength of a copper alloy without significantly degrading other desirable properties, such as uniform etching (in leadframe manufacture) and limited tool wear during stamping (in connecter manufacture).
- Copper alloy C 19400 has the composition, by weight, of 2.1%-2.6% iron, 0.05%-0.20% zinc, 0.015%-0.15% phosphorous and the balance copper. Alloy C 19400 has excellent stampability and an electrical conductivity of about 60% IACS (IACS stands for International Annealed Copper Standard and defines the conductivity of "pure" copper at 20°C as 100%).
- Another alloy, designated by the CDA as alloy C 19210 has the composition, by weight, of 0.05%-0.15% iron, 0.025%-0.04% phosphorous and the balance copper. Alloy C 19210 has an electrical conductivity of about 80% IACS, but relatively poor stampability.
- Magnesium is sometimes added to copper-iron-phosphorous alloys.
- the magnesium combines with phosphorous to form a magnesium phosphide that precipitates from the copper matrix as a discrete second phase particulate.
- a dispersion of magnesium phosphide particulate throughout the copper alloy increases the strength of the copper alloy and, by effectively removing phosphorous from solid solution with the copper, increases electrical conductivity.
- copper alloys containing magnesium, phosphorous and iron are known, there remains a need for a copper alloy with an improved combination of electrical conductivity, strength, stampability and resistance to stress relaxation.
- the copper alloy having an improved resistance to stress relaxation at temperatures of 105°C and above. It is a feature of the invention that the copper alloy contains controlled amounts of iron, phosphorous and magnesium with an effective amount of magnesium remaining in solution with the copper to favorably affect stress relaxation performance.
- the advantages of the copper alloy of the invention are that in excess of about 70% of the applied stress remains, in both the transverse and longitudinal directions, following exposure to 105°C for 3000 hours.
- the alloy has an electrical conductivity on the order of 80% IACS and is particularly suitable for use as an electrical connector.
- a copper alloy there is provided a copper alloy.
- the copper alloy contains, by weight, 0.05%-0.1% phosphorous, 0.05%-0.3% iron and the balance is copper and unavoidable impurities.
- the copper alloy further contains at least 0.06 weight percent of free magnesium in solution with the copper. The free magnesium effectively improves resistance to stress relaxation at elevated temperatures.
- Figure 1 schematically illustrates the transverse and longitudinal axes of a strip of copper alloy.
- Figure 2 shows in cross-sectional representation an electrical connector formed from the copper alloys of the invention.
- Figure 3 schematically illustrates an apparatus for stamping a copper alloy.
- Figure 4 illustrates in cross-sectional representation an evaluation of stampability.
- FIGS 5 and 6 graphically illustrate the criticality of magnesium content.
- Figure 7 illustrates the critical relationship between the percent phosphorous and the percent iron in a first alloy of the invention.
- Figure 8 illustrates the critical relationship between the percent phosphorous and the percent iron in a second, tin containing, alloy of the invention.
- Figure 9 illustrates a leadframe stamped from the copper alloys of the invention.
- Figures 10-12 graphically illustrate the effect of free magnesium on the percent stress remaining in the copper alloys of the invention.
- Figure 13 graphically illustrates the criticality of the magnesium content for good stampability.
- Figure 14 graphically illustrates exemplary alloys superimposed over the composition box of Figure 10.
- FIG. 2 illustrates in cross-sectional representation an electrical connector assembly 20 utilizing the copper alloys of the invention.
- the connector assembly 20 includes a socket 22 and a plug or jack 24.
- the socket 22 is formed from a strip of the copper alloy and bent into a desired shape, typically with a flat 26 for contacting the plug 24.
- a bend 28 generates an internal stress in the copper alloy strip drawing the flats 26 against the plug 24.
- room temperature nominally 25 °C
- this internal stress gradually dissipates and contact between the flats 26 and plug 24 deteriorates.
- the alloys of the invention better resist elevated temperature stress relaxation and produce an improved electrical connector.
- the iron content of the alloys of the invention is similar to that specified for copper alloy C 19700, by weight, 0.05%- 1.5% iron.
- the phosphorous content, 0.05%-0.17%, by weight, phosphorous, is at the low end of the range specified for copper alloy C 19700 to retain magnesium in solid solution with the copper.
- the iron content is between about 0.3% and 0.7% and most preferably, between about 0.35% and 0.50%.
- the phosphorous content is between 0.1% and 0.15%.
- the iron may be substituted with another transition metal such as manganese, cobalt, nickel and alloys thereof as a 1 :1 substitution, by weight.
- Good resistance to stress relaxation is accomplished by the presence of magnesium in solution with the copper.
- Magnesium in solution with the copper is referred to as "free magnesium” and is distinguished from magnesium in the form of magnesium phosphides (Mg P 2 ) that precipitate from the alloy matrix during processing. Magnesium that combines with phosphorous as phosphide particles has little or no effect on stress relaxation.
- iron, phosphorous and magnesium interact to determine th ⁇ . ⁇ o magnesium content.
- iron phosphides precipitate from the alloy matrix before the magnesium phosphides. If there is any magnesium left in solution after the phosphorous is completely precipitated as Fe 2 P and Mg 3 P 2 , this magnesium will favorably influence stress relaxation performance.
- the free magnesium content is calculated by first determining the amount of phosphorous available to combine with magnesium.
- Y is the free magnesium content and is a value greater than 0. While even trace amounts of free magnesium will increase the resistance to stress relaxation, to consistently obtain at least 70% stress remaining in a relief anneal (RA) temper after an exposure of 3000 hours at 105°C, at least about 0.03%, by weight of free magnesium should be present.
- RA relief anneal
- magnesium may cause cracking and sliver defects during hot rolling and the maximum magnesium content should be less than about 0.1%, by weight.
- the magnesium content will typically be between about 0.03% and 0.08%.
- the phosphorous content is maintained below 0.1 percent, by weight and the iron content maintained below 0.3 percent, by weight. Higher amounts of magnesium may then be included in the alloy without a severe loss of hot workability.
- the minimum amount of free magnesium is at least 0.06 weight percent, and inferably the free magnesium content is at least 0.07 weight percent.
- the total amount of magnesium in the alloy is less than 0.25 percent, by weight, and preferably less than 0.15 percent by weight. A most preferred magnesium content is between 0.1 weight percent and 0.15 weight percent.
- stampability When the copper alloy sheet is to be stamped into an intricate structure, such as a leadframe, one consideration is the stampability of the copper alloy sheet. Stampability may be rated by the percentage of break (fracture) versus shear at a stamped edge for a given punch to die clearance. Materials having good stampability exhibit relatively large values of percentage break over a broad range of tool clearances and increasing the percentage of break is associated with both reduced tool wear and reduced burr height.
- a method to evaluate stampability is schematically illustrated in Figure 3.
- a copper alloy strip 30 is supported by a die 32.
- a punch 34 reciprocates between the illustrated position and that indicated by the broken line 34', piercing the copper alloy strip 30. Both the die 32 and the punch 34 are formed from a material that is considerably harder than the copper alloy strip 30, such as tool steel.
- a clearance 36 is disposed between the punch 34 and die 32. Typically, the width of the clearance 36 is on the order of 10% of the thickness of the copper alloy strip 30.
- Figure 4 illustrates in cross-sectional representation an edge 38 of the copper alloy strip 30 following stamping.
- a first portion 40 of the edge 38 exhibits fracture, while a second portion 42 exhibits a sheared surface indicative of tool to strip contact.
- a measurement of the percent of thickness of the first portion 40 (A) to the overall thickness (B) of the copper alloy strip 30, provides the percentage of break:
- copper alloy C 19400 has about 25% break while copper alloy C 19210 has only about 15% break.
- Figure 5 graphically illustrates a critical magnesium content for the alloys of the invention when good stampability is desired.
- the alloys of the invention have both good stampability, approximately equivalent to or greater than C 19400, and an electrical conductivity in excess of about 70% IACS.
- the stampability limit lines 46 sufficient phosphorous is present to react with the available magnesium to form phosphides for good stampability.
- the stampability limit lines 46 insufficient phosphorous is present and poor stampability results.
- the electrical conductivity is below 70%. Within the composition box 44, the electrical conductivity is above about 70%.
- magnesium content from 0.02% to 0.03%, by weight, significantly opens the composition box of alloy compositions with good stampability. Increasing the magnesium content beyond 0.03% does not appear to provide any further benefit to stampability. So while 0.025% of magnesium provides some benefit, a preferred critical minimum magnesium content for the alloys of the invention is 0.03%, by weight. The maximum acceptable magnesium content of about 0.1%, by weight, beyond which cracking and sliver defects develop during hot rolling of the ingot.
- a preferred magnesium content of the alloys of the invention is, by weight, from 0.03% to 0.1% and a most preferred magnesium content is from 0.03% to 0.06%. While the phosphorous content of the alloys of the invention is described in detail below, the phosphide particulate size limit line 50 identifies that content of phosphorous above which large phosphide particles form.
- Figure 6 graphically illustrates the criticality of the magnesium content.
- stampability is equivalent to copper alloy C 19400.
- Above the line 46 is an excellent stampability region 54.
- Below the line 46 is a poor stampability region 56.
- Equation (4) was selected for the vertical axis because iron and phosphorous combine in approximately that ratio to form iron phosphide. It is desirable that there is sufficient phosphorous to combine with all the iron because iron remaining in solution in the copper matrix will reduce conductivity.
- the iron and phosphorous contents are defined by the composition box 58 graphically illustrated in Figure 7.
- the phosphorous content is less than 0.07%, the ultimate tensile strength of the alloy is less than about
- the maximum phosphorous content is defined by the phosphide particulate size limit line 50.
- the phosphorous content exceeds the limit defined by line 50, large, in excess of about 4 microns in diameter, particles form. These particles in the alloy microstructure may cause irregularities in the electroplated layers when the particles appear at the surface of the alloy material. The plating irregularities, such as blisters, are typically not acceptable for electrical applications.
- stampability limit line 46 Exceeding the stampability limit line 46, reduces stampability by the failure to provide an adequate number of magnesium phosphide particles. Below the conductivity limit line 48, excess phosphorous remains in solid solution with the copper and electrical conductivity is below 70% IACS.
- the phosphorous content of the high stampability alloys of the invention is, by weight, from 0.07% to 0.16% and the iron content from
- composition box defined by the weight percent coordinates of (0.05% Fe, 0.07% P), (0.21% Fe, 0.07% P), (0.21% Fe, 0.16%
- More preferred iron and phosphorous contents are defined by the composition box 64, centered around a target 66 of 0.115% phosphorous and 0.25% iron and defined by the coordinates (0.14% Fe, 0.1 % P), (0.27% Fe,
- alloys of the invention are disclosed as containing iron, it is within the scope of the invention for up to 50% of the iron to be replaced with another transition metal, such as manganese, nickel, cobalt or mixtures thereof, on a 1 : 1 basis by weight.
- another transition metal such as manganese, nickel, cobalt or mixtures thereof
- the sulphur content of the alloy should be less than about 10 ppm, and preferably less than 7 ppm.
- the size and frequency of plating nodules decreases with decreasing sulphur content. Nodules smaller than 0.05 millimeter are considered acceptable in most applications, thus requiring that the sulphur content be held to below about 10 ppm.
- Tin is a preferred addition to the alloys of the invention.
- the addition of tin increases strength, but typically reduces electrical conductivity as well.
- the tin content is, by weight, from 0.05% to 0.35% and more preferably from 0.10% to 0.20%.
- the addition of 0.15% of tin narrows the composition box 68 to the coordinates of (0.05% Fe, 0.02% P), (0.05% Fe - 0.033% P), (0.35% Fe, 0.14% P) and (0.43% Fe, 0.13% P).
- additions that may be made to the alloys of the invention include aluminum, antimony and zinc.
- the total cumulative content of these other additions is less than about 1%, by weight, such that the desired properties of the alloy, notably conductivity, are not detrimentally affected.
- a leadframe 70 is stamped from a sheet of copper alloy, typically having a thickness of between 0.13 mm (0.005 inch) and 0.25 mm (0.01 inch) to form features such as leads 72 and die paddle 74.
- the lead to lead pitch is on the order of the thickness of the sheet mandating the use of a copper alloy with good stampability.
- Copper alloys having the compositions specified in Table 1 were cast as 4.5 kg (10 pound) ingots and rolled to a final gage of 0.51 mm (0.02 inch).
- a hard/relief anneal temper was obtained by the process steps of hot roll, diffusion anneal at 600°C, cold roll, anneal at 525°C, roll to final gage and then relief anneal at 250°C for from 2 to 8 hours.
- the resistance to stress relaxation of the strips was then evaluated by constraining a cantilever beam formed from the copper alloy to a fixed deflection and measuring the load exerted by the beam on the constraint as a function of time at temperature.
- the initial stress at the surface of the test sample was set to 80% of the room temperature 0.2% offset yield strength.
- the percent stress remaining in both the longitudinal and transverse directions increases as a function of the free magnesium content.
- the free magnesium content exceeds about 0.03%, by weight, at least 70% stress remains after 3000 hours exposure at 105°C in both the longitudinal and transverse directions.
- Sample H586 illustrates the unique properties of the alternative embodiment disclosed above.
- the alloy has an iron content of 0.14 weight percent, a phosphorous content of 0.07 weight percent and a free magnesium content of 0.073 weight percent.
- the alloy is readily hot workable, has a high electrical conductivity, 88% IACS and good resistance to stress relaxation.
- Figure 10 illustrates the percent stress remaining following exposure at 105°C for 3000 hours for copper alloys of the invention in the hard/relief anneal temper as a function of the free magnesium content.
- the steeper slope for the percentage of stress remaining along the transverse direction indicates that the free magnesium has a greater effect on resistance to stress relaxation for connector components oriented in that direction than on connector components oriented in the longitudinal direction. This is believed due to the interaction of the free magnesium with the dislocation microstructure such that the crystallographic texture becomes less significant.
- the enhanced benefit in the transverse orientation is particularly beneficial since most components are stamped transverse to the rolling direction of the copper strip.
- Figure 11 illustrates that increasing the amount of free magnesium also improves the stress relaxation resistance at the higher temperature of 125°C following a 3000 hour exposure.
- OS. grain size in microns.
- UTS room temperature ultimate tensile strength
- Copper alloys of the compositions specified in Table 2 were cast and rolled to strip having a final gage of 0.51 mm (0.02 inch).
- the alloys were imparted with a hard temper by the process steps of hot rolling, cold rolling, annealing at 500°C - 600°C, cold roll, anneal at 450°C - 525°C, then cold roll to gage with a minimum total reduction following the last anneal of about 30%.
- Table 2 illustrates that the presence of free magnesium improves the resistance to stress relaxation of the copper alloys in the hard temper.
- the enhancement to resistance to stress relaxation is again more pronounced in the transverse direction as compared to the longitudinal direction.
- the inclusion of free magnesium improves the resistance to stress relaxation in bends formed along either axis.
- Example 3 Copper alloys containing magnesium, phosphorous and iron were cast as 4.5 kg
- Figure 13 illustrates the percentage of break by the numerical value next to each point and shows that when the magnesium content exceeds 0.03% and an excess of phosphorous is present, excellent stampability is achieved.
- the magnesium content is less than 0.03%, progressively more phosphorous is required to achieve good stampability.
- Increasing the phosphorous content leads to the risk of both large phosphide particles and phosphorous remaining in solution and deteriorating electrical conductivity.
- Figure 14 graphically illustrates the alloys of Table 3 superimposed on composition box 58 of Figure 7.
- Alloys A-E the alloys of the invention, are within the composition box 58 and have an ultimate tensile strength, percent conductivity, percent break and phosphide size within the preferred ranges specified above.
- Alloys F-K are outside the composition box 58 and have one or more properties that do not meet the preferred ranges. Those values outside the preferred ranges are underlined in Table 3. It is apparent that there has been provided in accordance with the invention a copper alloy that fully satisfies the objects, means and advantages set forth hereinabove.
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Abstract
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU81821/98A AU8182198A (en) | 1997-07-22 | 1998-07-06 | Copper alloy having magnesium addition |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/898,053 US5868877A (en) | 1997-07-22 | 1997-07-22 | Copper alloy having improved stress relaxation |
US08/898,053 | 1997-07-22 | ||
US08/898,694 | 1997-07-22 | ||
US08/898,694 US5980656A (en) | 1997-07-22 | 1997-07-22 | Copper alloy with magnesium addition |
US09/099,297 US6093265A (en) | 1997-07-22 | 1998-06-18 | Copper alloy having improved stress relaxation |
US09/099,297 | 1998-06-18 |
Publications (1)
Publication Number | Publication Date |
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WO1999005331A1 true WO1999005331A1 (fr) | 1999-02-04 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US1998/013925 WO1999005331A1 (fr) | 1997-07-22 | 1998-07-06 | Alliage de cuivre au magnesium |
Country Status (2)
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AU (1) | AU8182198A (fr) |
WO (1) | WO1999005331A1 (fr) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1078995A1 (fr) * | 1999-08-25 | 2001-02-28 | Kabushiki Kaisha Kobe Seiko Sho | Alliage de cuivre pour pièces électriques ou électroniques |
EP1482063A1 (fr) * | 2003-05-27 | 2004-12-01 | Fisk Alloy Wire, Inc. | Fabrication d'alliages de cuivre-magnésium et fil de cuivre amelioré |
EP1674587A1 (fr) * | 2004-12-24 | 2006-06-28 | Kabushiki Kaisha Kobe Seiko Sho | Alliage de cuivre avec aptitude au pliage et resistance à la relaxation en contraintes ameliorées |
AU2001277686B2 (en) * | 2000-08-01 | 2006-07-20 | Sigma-Tau Industrie Farmaceutiche Riunite S.P.A. | Use of fibrates for the preparation of a medicament useful in the treatment of congestive heart failure |
CN100342054C (zh) * | 2005-12-30 | 2007-10-10 | 东北大学 | 一种电力机车受电弓滑板材料及其制备方法 |
EP1918390A1 (fr) * | 2005-07-07 | 2008-05-07 | Kabushiki Kaisha Kobe Seiko Sho | Alliage de cuivre de grande résistance et d excellente faculté de traitement en torsion et processus de fabrication de feuille d alliage de cuivre |
CN100439530C (zh) * | 2004-12-24 | 2008-12-03 | 株式会社神户制钢所 | 具有弯曲性和应力弛豫性能的铜合金 |
EP2048251A1 (fr) * | 2006-05-26 | 2009-04-15 | Kabushiki Kaisha Kobe Seiko Sho | ALLIAGE DE CUIVRE TRÈS RÉSISTANT PRÉSENTANT UNE CONDUCTIVITÉ ÉLECTRIQUE ÉLEVÉE ET UNE EXCELLENTE MALLÉABILITÉ EN fLEXION |
CN115735018A (zh) * | 2020-06-30 | 2023-03-03 | 三菱综合材料株式会社 | 铜合金、铜合金塑性加工材、电子电气设备用组件、端子、汇流条、引线框架及散热基板 |
CN116411195A (zh) * | 2023-04-19 | 2023-07-11 | 云南大学 | 一种铜镁合金制备中镁含量的控制方法 |
US12203158B2 (en) | 2020-06-30 | 2025-01-21 | Mitsubishi Materials Corporation | Copper alloy, copper alloy plastic working material, component for electronic/electrical device, terminal, bus bar, lead frame, and heat dissipation substrate |
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US3677745A (en) * | 1969-02-24 | 1972-07-18 | Cooper Range Co | Copper base composition |
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Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6344171B1 (en) | 1999-08-25 | 2002-02-05 | Kobe Steel, Ltd. | Copper alloy for electrical or electronic parts |
EP1078995A1 (fr) * | 1999-08-25 | 2001-02-28 | Kabushiki Kaisha Kobe Seiko Sho | Alliage de cuivre pour pièces électriques ou électroniques |
AU2001277686B2 (en) * | 2000-08-01 | 2006-07-20 | Sigma-Tau Industrie Farmaceutiche Riunite S.P.A. | Use of fibrates for the preparation of a medicament useful in the treatment of congestive heart failure |
EP1482063A1 (fr) * | 2003-05-27 | 2004-12-01 | Fisk Alloy Wire, Inc. | Fabrication d'alliages de cuivre-magnésium et fil de cuivre amelioré |
EP1674587A1 (fr) * | 2004-12-24 | 2006-06-28 | Kabushiki Kaisha Kobe Seiko Sho | Alliage de cuivre avec aptitude au pliage et resistance à la relaxation en contraintes ameliorées |
CN100439530C (zh) * | 2004-12-24 | 2008-12-03 | 株式会社神户制钢所 | 具有弯曲性和应力弛豫性能的铜合金 |
EP2439296A3 (fr) * | 2005-07-07 | 2012-10-17 | Kabushiki Kaisha Kobe Seiko Sho | Alliage de cuivre haute résistance et maniabilité de pliage supérieure, et procédé de fabrication de plaques d'alliage en cuivre |
EP1918390A1 (fr) * | 2005-07-07 | 2008-05-07 | Kabushiki Kaisha Kobe Seiko Sho | Alliage de cuivre de grande résistance et d excellente faculté de traitement en torsion et processus de fabrication de feuille d alliage de cuivre |
US9976208B2 (en) | 2005-07-07 | 2018-05-22 | Kobe Steel, Ltd. | Copper alloy with high strength and excellent processability in bending and process for producing copper alloy sheet |
EP1918390A4 (fr) * | 2005-07-07 | 2009-09-30 | Kobe Steel Ltd | Alliage de cuivre de grande résistance et d excellente faculté de traitement en torsion et processus de fabrication de feuille d alliage de cuivre |
CN100342054C (zh) * | 2005-12-30 | 2007-10-10 | 东北大学 | 一种电力机车受电弓滑板材料及其制备方法 |
US8268098B2 (en) | 2006-05-26 | 2012-09-18 | Kobe Steel, Ltd. | Copper alloy having high strength, high electric conductivity and excellent bending workability |
EP2048251A4 (fr) * | 2006-05-26 | 2009-10-14 | Kobe Steel Ltd | ALLIAGE DE CUIVRE TRÈS RÉSISTANT PRÉSENTANT UNE CONDUCTIVITÉ ÉLECTRIQUE ÉLEVÉE ET UNE EXCELLENTE MALLÉABILITÉ EN fLEXION |
US8357248B2 (en) | 2006-05-26 | 2013-01-22 | Kobe Steel, Ltd. | Copper alloy having high strength, high electric conductivity and excellent bending workability |
US9177686B2 (en) | 2006-05-26 | 2015-11-03 | Kobe Steel, Ltd. | Copper alloy having high strength, high electric conductivity and excellent bending workability |
EP2048251A1 (fr) * | 2006-05-26 | 2009-04-15 | Kabushiki Kaisha Kobe Seiko Sho | ALLIAGE DE CUIVRE TRÈS RÉSISTANT PRÉSENTANT UNE CONDUCTIVITÉ ÉLECTRIQUE ÉLEVÉE ET UNE EXCELLENTE MALLÉABILITÉ EN fLEXION |
CN115735018A (zh) * | 2020-06-30 | 2023-03-03 | 三菱综合材料株式会社 | 铜合金、铜合金塑性加工材、电子电气设备用组件、端子、汇流条、引线框架及散热基板 |
CN115735018B (zh) * | 2020-06-30 | 2024-01-26 | 三菱综合材料株式会社 | 铜合金、铜合金塑性加工材、电子电气设备用组件、端子、汇流条、引线框架及散热基板 |
US12203158B2 (en) | 2020-06-30 | 2025-01-21 | Mitsubishi Materials Corporation | Copper alloy, copper alloy plastic working material, component for electronic/electrical device, terminal, bus bar, lead frame, and heat dissipation substrate |
CN116411195A (zh) * | 2023-04-19 | 2023-07-11 | 云南大学 | 一种铜镁合金制备中镁含量的控制方法 |
Also Published As
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