CN1688732B - Age-hardening copper-base alloy and processing process - Google Patents
Age-hardening copper-base alloy and processing process Download PDFInfo
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- CN1688732B CN1688732B CN038244713A CN03824471A CN1688732B CN 1688732 B CN1688732 B CN 1688732B CN 038244713 A CN038244713 A CN 038244713A CN 03824471 A CN03824471 A CN 03824471A CN 1688732 B CN1688732 B CN 1688732B
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
Abstract
An age-hardening copper-base alloy and processing method to make a commercially useful strip product for applications requiring high yield strength and moderately high electrical conductivity, in a strip, plate, wire, foil, tube, powder or cast form. The alloys are particularly suited for use in electrical connectors and interconnections. The alloys contain Cu-Ti-X where X is selected from Ni, Fe, Sn, P, Al, Zn, Si, Pb, Be, Mn, Mg, Ag, As, Sb, Zr, B, Cr and Co. and combinations thereof. The alloys offer excellent combinations of yield strength, and electrical conductivity, with excellent stress relaxation resistance. The yield strength is at least of 724 MPa (105 ksi) and the electrical conductivity is at least 50% IACS.
Description
But the present invention relates to a kind of age hardening type copper base alloy and a kind of processing method by this alloy preparation commercial product.More specifically, adopt a kind of processing method that comprises the solution annealing in the technological process and at least aging anneal that the copper alloy of 0.35-5 weight % titanium is processed into final dimension.The electroconductibility of the product that obtains is higher than 50%IACS, and yield strength is higher than 724MPa (105ksi).
In the whole present patent application, except as otherwise noted, all compositions are weight %, and all machinery and Experiments of Electricity are all carried out under room temperature (nominally 22 ℃).Speech " approximately " means ± 10%, mean the specific fundamental element that contains 50 weight % in the alloy at least as the speech in the copper base " base ".Term " rolling " intention comprise stretching or drawing or for example make and processing wire rod, bar or tubing in the cold working of any other form of using.
Many dissimilar electric cuplers adopt copper base alloy to make.For electric cupler, important performance comprises yield strength, bend formability, stress relaxation drag, Young's modulus, ultimate tensile strength and electroconductibility.
The target value of these performances and their relative importance depend on the predetermined use occasion of the product that adopts described copper alloy manufacturing.Following performance specification is general the introduction for many predetermined occasions, and still, for car engine cover purposes, described target value is concrete.
Yield strength is that bill of material reveals the stress when departing from proportionlity special tolerances between the stress and strain, and typical deviation is 0.2%.This is the stress sign when one viscous deformation becomes principal mode for recoverable deformation.It is desirable to, as the yield strength of the copper alloy of junctor 724MPa at least.
When applied stress effect sheet metal strip in use, for example when band when bending to after the junctor carry load, it is obvious that stress relaxation becomes.Metal is by producing equal and opposite in direction but the opposite internal stress of direction produces retroaction.If metal remains on strain location, then internal stress is as the function of time and temperature and reduce.The reason that this phenomenon occurs is to make the recoverable strain in the metal be transformed into plasticity or permanent strain by microplasticity is mobile.
Copper base electric cupler must remain on its component under the condition that is higher than critical contact force long-time, to obtain good electrical connection.Stress relaxation is reduced to below the critical load contact force, causes forming open circuit.For the copper alloy that is used for the junctor purposes, it is desirable to still keep at least 95% initial stress following 1000 hours the time when being exposed to 105 ℃, and, still keep at least 85% initial stress following 1000 hours the time when being exposed to 150 ℃.
Young's modulus is also referred to as Young's modulus, is measuring of metal rigidity or rigidity, and it is at elastic region stress and corresponding strained ratio.Because Young's modulus is measuring of rigidity of material, therefore, it is desirable to have magnitude and reaches 140GPa (20x10
3Ksi) high-modulus.
Flexible decision minimum bending radius (MBR), it is determining crooked severity do not occurring can implementing under the rimose situation along crooked sheet metal strip external diameter direction.For forming different shapes and having for the junctor of bending of various angles, MBR is a key property.
Bending forming can be expressed as MBR/t, and wherein, t is a sheet metal strip thickness.MBR/t is the axle minimum profile curvature radius that centered on when not destroying of bending metals band and the ratio of thickness of strip.At exercise question be
Standard Test Method for Semi-Guided Bend Test for Ductility of Metallic MaterialsASTM (American Society forTesting and Materials) numbering E290-92 in described " axle " experiment is had been described in detail.
It is desirable to, the basic isotropy of MBR/t, it all has similar value at bending axis vertical with sheet metal strip rolling direction " good direction " and at bending axis " difference direction " parallel with sheet metal strip rolling direction.It is desirable to MBR/t for 90 ° of bendings, it is worth about 1.5 or littler, and for 180 ° of bendings, it is worth about 2 or littler.
Perhaps, can have the test block of V-type groove and have the drift of the working-surface of requirement radius, estimate 90 ° of bending formings when crooked by use.In described " V-type test block " method, state copper alloy band to be tested is placed between test block and the drift, when the driving drift enters groove, in band, form the degree of crook that requires.
Relevant with described " V-type test block " method is in 180 ° of " forming punch " methods, adopts the drift with cylindrical working-surface to make copper alloy band that 180 ° of bendings take place.
At exercise question be
Standard Test Method for Bend Test for Formability Of Copper Alloy Spring MateriaAll described " V-type test block " and " forming punch " method are had been described in detail among the ASTM numbering B820-98 of l.
For a given metal sample, two kinds of methods all provide can quantitative bending property result, and, can use any method to determine relative bending property.
Ultimate tensile strength is ultimate load and the long-pending ratio of band initial cross sectional that bore before band during the stretching experiment lost efficacy.It is desirable to the about 760MPa of ultimate tensile strength.
Electroconductibility adopts %IACS (International Annealed Copper Standard) expression, wherein, during with 20 ℃ not the electroconductibility of the copper of alloying be defined as 100%IACS.
In the various documents, United States Patent (USP) 4,601,879 and 4,612,167 disclose titaniferous copper base alloy.Described patent 4,601,879 disclosed copper base alloys contain 0.25-3.0% nickel, 0.25-3.0% tin and 0.12-1.5% titanium.The electroconductibility of exemplary alloy is 48.5-51.4%IACS, and yield strength is 568.8-579.2MPa (82.5-84ksi).
Described patent 4,612,167 disclosed copper alloys contain 0.8-4.0% nickel and 0.2-4.0% titanium.The electroconductibility of exemplary alloy is 51%IACS, and yield strength is 663.3-679.2MPa (96.2ksi-98.5ksi).
AMAX Copper, (Greenwich, CT) business-like copper Ni-Ti alloy has the name composition of Cu-2%Ni-1%Ti and Cu-5%Ni-2.5%Ti to Inc..In the Cu-2%Ni-1%Ti alloy property of being reported, yield strength is 441.3-551.6MPa (64-80ksi), and ultimate tensile strength is 503.3-655.0MPa (73-95ksi), and unit elongation is 9%, and electroconductibility is 50-60%IACS.In the Cu-5%Ni-2.5%Ti alloy property of being reported, yield strength is 620.6-689.5MPa (90-100ksi), and ultimate tensile strength is 744.7MPa (108ksi) UTS, and unit elongation is 10%, and electroconductibility is 40-53%IACS.
For described copper alloy, many current and following application scenarios all require electroconductibility 50%IACS at least, and yield strength is 724MPa (105ksi) at least.Still need electroconductibility and the copper-titanium alloy of intensity and the method for preparing described alloy that can obtain to require.
Summary of the invention
In the present invention, a kind of age hardening type copper base alloy is provided, and described alloy is processed into the method for the commercial product of any purposes that can be used for requirement high strength and high electrical conductivity, the canonical form of product comprises band, sheet material, wire rod, foil, tubing, powder or foundry goods.When the method according to this invention adds man-hour, described alloy obtains the yield strength of 724MPa (105ksi) and the electroconductibility of 50%IACS at least, makes alloy be particularly suitable for electric cupler and cross tie part.
Described alloy basic composition is (by weight) 0.35-5% titanium, the X of 0.001-10%, wherein, X is selected from Ni, Fe, Sn, P, Al, Zn, Si, Pb, Be, Mn, Mg, Bi, S, Te, Se, Ag, As, Sb, Zr, B, Cr and Co and their combination the rest is copper and unavoidable impurities.The electroconductibility of alloy is 50%IACS at least, and yield strength is 105ksi at least.
Of the present invention one preferred aspect, alloy basic composition is 0.35-2.5% titanium, 0.5-5.0% nickel, 0.5-0.8% iron, cobalt and composition thereof, 0.01-1.0% magnesium, maximum 1% Cr, Zr, Ag and their combination the rest is copper and unavoidable impurities.
When not having beryllium, these alloys can avoid occurring the problem of the possible health risk relevant with present beryllium copper, simultaneously, can provide the combination of similar intensity and electroconductibility again.
The summary of several accompanying drawings
Fig. 1 is the schema of the method for first kind of processing copper alloy of the present invention of explanation.
Fig. 2 is the schema of the method for second kind of processing copper alloy of the present invention of explanation.
Fig. 3 is the schema of the method for the third processing of explanation copper alloy of the present invention.
Detailed Description Of The Invention
Many electric currents carry the purposes requirement to have the copper alloy with good formability and stress relaxation drag of the combination of intensity and electric conductivity. Two exemplary purposes are automobile purposes and the multimedia purposes (such as computer, DVD player, CD reading machine etc.) under hood.
For the automobile purposes, require copper alloy have good formability, at least 50%IACS electric conductivity and be up to 200 ℃ stress relaxation drag. For multimedia interconnection purposes, require the yield strength of copper alloy to surpass 724MPa (105ksi), electric conductivity is higher than 50%IACS, and the mechanical stability under the operating temperature of room temperature and a little higher than room temperature, it is characterized in that having excellent stress relaxation drag under about 100 ℃.
When adopting method of the present invention to add man-hour, described alloy composition unexpectedly provides and satisfies automobile and multimedia purposes, and the optimum performance that other Electrical and Electronic purposes require makes up. Described alloy can provide higher intensity and high electric conductivity simultaneously, and higher electric conductivity and high intensity are provided simultaneously.
Contain Cu-Ti-X in the alloy composition of the present invention, wherein, X is selected from Ni, Fe, Sn, P, Al, Zn, Si, Pb, Bi, S, Te, Se, Be, Mn, Mg, Ag, As, Sb, Zr, B, Cr and Co and their combination. Ti content is 0.35-5%, and the total amount of element " X " is 0.001-10%.
When X is selected from Ni, Fe, Co, Mg, Cr, Zr, when Ag and their mixture, intensity and electroconductibility are the highest.
Can contain aerobic, sulphur and carbon with the typical content in electrolysis (negative electrode) copper or remelting copper or the copper alloy scrap in the alloy of the present invention.Typically, the amount of every kind of described element is about 2-50ppm, and preferred every kind of amount is lower than 20ppm.
Also can comprise other interpolation elements that influence alloy property.This class is added the element that element comprises the free machining property of improving alloy, for example bismuth, lead, tellurium, sulphur and selenium.When adding in order to improve free machining property, the amount of described additive can be up to 2%.The total amount of preferred free machining property additive is about 0.8%-1.5%.
Copper alloy, particularly the exemplary impurity total content that exists in the copper alloy that is become by recovery or waste material copper can be up to about 1%.As enumerating of a non-limit, described impurity comprises magnesium, aluminium, silver, silicon, cadmium, bismuth, manganese, cobalt, germanium, arsenic, gold, platinum, palladium, hafnium, zirconium, indium, antimony, chromium, vanadium and beryllium.The amount of every kind of impurity should be lower than 0.35%, preferably is lower than 0.1%.
Should be realized that: when the content of some above-mentioned impurity or other elements and when afore mentioned rules impurity scope is overlapping, may be favourable to copper alloy of the present invention.For example, can improve intensity or punching performance.The invention is intended to comprise the additive of these low levelss.
In a preferred embodiment of the present invention, titanium content is 0.35-2.5%, and in a most preferred embodiment, titanium content is 0.8-1.4%.
When titanium was present in the copper alloy matrix with the solid solution form, electroconductibility seriously descended." X " should preferably make titanium separate out from the solid solution attitude during aging anneal effectively.Be used to promote described suitable " X " element of separating out to comprise Ni, Fe, Sn, P, Al, Si, S, Mg, Cr, the combination of Co and these elements.
A kind of preferred interpolation element is a nickel.The combination results precipitate CuNiTi of Ni and Ti, and the existence of Fe and Ti produces precipitate Fe
2Ti.
Another kind of preferred interpolation element is a magnesium.Add the stress relaxation drag and the softening drag of Mg raising final size and state product.Mg also can provide softening drag during the aging anneal thermal treatment in technological process.
When amount is low, add element Cr, Zr and/or Ag can improve intensity, but can excessively not reduce electroconductibility.
The preferred alloy of the present invention of a kind of yield strength with improvement, electroconductibility, stress relaxation drag and the suitably flexible combination of (modest) basic composition is about 0.5-5.0% nickel, about 0.35-2.5% titanium, about 0.5-0.8% iron or cobalt, about 0.01-1.0% magnesium, choose wantonly maximum about 1.0% one or more be selected from Sn, P, Al, Zn, Si, Pb, Bi, S, Te, Se, Be, Mn, Mg, Ag, As, Sb, Zr, B, Cr and their mixture, and, the rest is copper and impurity.Preferred described optional elements comprise at most about 1% one or more be selected from Cr, the element of Zr and Ag.
The more preferably scope of this alloy is: about 0.8-1.7% nickel, about 0.8-1.4% titanium, about 0.90-1.10% iron or cobalt, about 0.10-0.40% magnesium, at most about 1.0% one or more be selected from Cr, Zr, the element of Ag or Sn and their mixture the rest is copper and impurity.
In first embodiment of the present invention, described alloy composition and the yield strength that provides of processing be at least about 793MPa (115ksi), and preferably at least about 827MPa (120ksi).For this embodiment, the highest about 40%IACS of electroconductibility.In second embodiment of the present invention, the yield strength that described composition and processing provide is higher than about 724MPa (105ksi), and preferably is up to few about 793MPa (115ksi).In this second embodiment, the preferably about 45-55%IACS of the electroconductibility of alloy.In the 3rd embodiment, the yield strength that described composition and processing provide is about 552-690MPa (80-100ksi), the about 55-65%IACS of electroconductibility.
Fig. 1 shows the technology of first embodiment according to the present invention with the schema form.Adopt traditional method that alloy of the present invention is carried out melting and casting 10.At about 750-1000 ℃ of following hot rolling 12 described cast alloy.After oxide compound is removed in grinding, alloy is carried out cold rolling 14, be about 50-99% wherein with the vertical cross-sectional area draught of rolling direction (" area reduction ").Then, can be to alloy solution treatment 16 under about 850-1000 ℃ solution annealing temperature, the time is from about 10 seconds to about 1 hour, subsequently, quenches 18 or be chilled to envrionment temperature soon, obtains the equiax crystal of the about 5-20 μ of average grain size m.Afterwards, it is cold rolling 20 to carry out the first time to alloy, and its area is depressed more about 80% than the highest, preferably about 30-80%.For the first time after cold rolling 20, carry out annealing 22 the first time, annealing temperature is about 400-650 ℃, and preferably about 450-600 ℃, the time is from about 1 minute to 10 hours, preferably about 1-8 hour.Then, it is cold rolling 24 that alloy is carried out the second time, depresses than being cold-rolled to final dimension with the area of about 10-50%.After for the second time cold rolling, can carry out annealing 26 the second time, annealing temperature is about 150-600 ℃, and preferably about 200-500 ℃, the time was from about 15 seconds to about 10 hours.
Perhaps, according to another embodiment of the invention, described alloy is processed into during the final size, not the solution heat treatment in the adopting process process.That is: can alloy be processed into final size by anneal and the intervenient cold worked circulation of using (a plurality of) lesser temps.This selectable method is particularly useful for the higher product of preparation electroconductibility.
Fig. 2 shows another selectable technology of the present invention with the schema form.Adopt traditional method that alloy of the present invention is carried out melting and casting 10.At about 750-1000 ℃ of following hot rolling 12 described cast alloy, and, quench subsequently or cooling fast.After oxide compound is removed in grinding, the alloy after the described hot rolling is carried out cold rolling 14, wherein area is depressed than being about 50-99%.Then, can be under about 400-650 ℃ annealing temperature alloy be carried out anneal 28 first time, the time was from about 15 seconds to about 10 hours.If desired, described cold rolling and for the first time annealing steps can randomly repeat.Subsequently, alloy is carried out area depress cold rolling 30 than for about 40-80%, afterwards,, under preferably about 450-600 ℃ temperature, carry out annealing 32 the second time preferably about 1-10 hour of time at about 400-650 ℃.Then, with the area of about 10-50% depress than with alloy cold rolling 34 to final dimension.Randomly, afterwards, can be at about 150-600 ℃, preferably about 200-500 ℃ of following enforcement anneals 26 for the third time, and the time was from about 15 seconds to about 10 hours.
Can select the alternate preferred embodiment to use for second of technology of the present invention and form the alloy that is in preferable range.The alloy of the present invention that this technology can prepare has the nominal performance of about 758MPa (110ksi) YS (yield strength) and about 50%IACS electroconductibility.With reference to Fig. 3, adopt traditional method that alloy is carried out melting and casting 10.At about 750-1000 ℃ of following hot rolling 12 described cast alloy.After oxide compound is removed in grinding, depress ratio with the area of about 50-99%, the alloy after the described hot rolling is carried out cold rolling 14.Then, to alloy solution treatment 16, the time was from about 15 seconds to about 1 hour under about 950-1000 ℃.Next, depress ratio, described alloy is carried out cold rolling 20, then, carry out annealing 28 the first time with the area of about 40-60%, the about 400-650 of annealing temperature ℃, preferably about 450-600 ℃, about 1-10 of time hour, preferably about 1-3 hour.Anneal after 28 for the first time, adopt the area of about 40-60% to depress than carrying out cold rolling 30.Then, under than the 28 low temperature of annealing for the first time, alloy is carried out annealing 32 the second time.Annealing for the second time under about 375-550 ℃ about 1-3 hour.Then, depressing ratio at least about 30% area, with described through twice annealed alloy cold rolling 34 to final dimension, wherein, alloy can be at about 150-600 ℃, anneals 26 for the third time, about 1-3 of time hour under preferably about 200-500 ℃.
With reference to the following examples, will understand alloy of the present invention and technology of the present invention better.
Embodiment
In the embodiment that follows some technology description, performance and unit all adopt contraction.For example, "=inch, WQ=shrend; slash mark /=continue (for); the SA=solution annealing, CR=is cold rolling or cold pressing down YS=yield strength; TS=tensile strength; EL=unit elongation, %IACS=electroconductibility, the ratio of MBR/t=minimum bending radius and thickness of strip; SR=stress relaxation drag, the Gs=grain-size, μ m=micron, beg.=begins, the recr.=recrystallize, n.c.r.=is perfect recrystallization not, sec. or s=second, hrs. or h=hour, MS/m=1,000,000 siemens/rice, ksi=kip/square inch.
Embodiment 1
Adopt method shown in Figure 1, melting and employing Durville casting cast out a series of 4.5kg (10 pounds) laboratory ingot castings of analyzing composition shown in the table 1 that have in punching block in quartz crucible.After cast, ingot casting is of a size of 10.16cmx10.16cmx4.45cm (4 " X4 " X1.75 ").After 950 ℃ were incubated 3 hours down, (1.1 ") reheated 10 minutes under 950 ℃, and (0.50 ") afterwards, carried out shrend to adopt 3 passages further to be hot-rolled down to 1.27cm to adopt 3 passages that ingot casting is hot-rolled down to 2.8cm.By in 1000 ℃ of insulations hot rolled plate homogenizing processing to being obtained in 2 hours, afterwards, carry out shrend.Remove after the zone of oxidation through finishing and grinding, alloy is cold-rolled to 1.27mm (0.050 ").Then, alloy is 1000 ℃ of following solution treatment 20-60 seconds, alloy J 346 exceptions just, and this alloy was 950 ℃ of solution treatment 60 seconds.After solid solution and the quench treatment, with (0.025 "), and under the alloy cold rolling 50% to 0.64mm 550 ℃ of following aging anneals 3 hours.Then, with under the alloy cold rolling 50% to 0.32mm (0.0125 ") size, and, 275 ℃ of following stress relief annealings 2 hours.Table 2 has provided the measuring result of performance.
Table 2 data show: obtained the high-yield strength of 621-765MPa (90-111ksi) and the electroconductibility of 38.2-63.8%IACS.Cu-Ni-Ti-Fe alloy J345 and J346 are approaching in the expected value of 105 ℃ of stress relaxation drags that obtain after following 1000 hours and 95%.Cu-Ni-Ti-Mg alloy J354 has then reached this expected value.
Embodiment 2
According to technology as shown in Figure 2, as embodiment 1, the alloy in the his-and-hers watches 1 is processed, the homogenizing thermal treatment after experience obtains the hot rolled plate size.Among this embodiment, alloy is machined to final dimension, not the solution heat treatment in the adopting process process.Remove after the zone of oxidation through finishing and grinding, alloy is cold-rolled to 2.54mm (0.100 "), and carry out 3 hours the aging anneal first time under 550 ℃.Then, with (0.030 "), and under 525 ℃, carry out 3 hours the aging anneal second time under the alloy cold rolling 70% to 0.76mm.Then, with under the alloy cold rolling 50% to 0.38mm (0.015 ") size, and, 275 ℃ of following stress relief annealings 2 hours.Measurement performance in this case, the result is as shown in table 3.
With the data consistent in the table 2, the alloy of this embodiment has the high-yield strength of 676-738MPa (98-107ksi) and the more high conductivity of 49.9-69.7%IACS simultaneously.When adding Fe or Mg in the Cu-Ni-Ti base alloy, the stress relaxation drag increases.Relatively alloy J354 and alloy J351 can be found out by data in the table 3: when adding Mg in the Cu-Ni-Ti alloy, can obtain the highest stress relaxation drag.
Embodiment 3
According to technology as shown in Figure 1, melting and employing Durville casting cast out a series of 4.5kg (10 pounds) laboratory ingot castings of analyzing composition shown in the table 4 that have in punching block in quartz crucible.After cast, ingot casting is of a size of 10.16cmx10.16cmx4.45cm (4 " X4 " X1.75 ").After 950 ℃ were incubated 3 hours down, (1.1 ") were thick, reheat 10 minutes under 950 ℃, and (0.50 ") is thick, afterwards, carries out shrend to adopt 3 passages further to be hot-rolled down to 1.27cm to adopt 3 passages that ingot casting is hot-rolled down to 2.8cm.Remove after the zone of oxidation through finishing and grinding, alloy is cold-rolled to 1.27mm (0.050 ").
Then, alloy that will be except that J477 afterwards, carries out shrend 1000 ℃ of following solution treatment 25 seconds, serves as the controlled tiny recrystallization crystal particle dimension of about 12-24 μ m to obtain diameter.The treatment process of alloy J477 is: 25 seconds+WQ of 950 ℃ of following solution heat treatment obtains the grain-size of 9 μ m.
With (0.025 ") is thick, and carries out aging anneal under 550 ℃, and this annealed time can excessively not make the electroconductibility maximum under the remollescent situation at matrix effectively under all alloy cold rollings 50% to 0.64mm.Soaking time under 550 ℃ is as shown in table 5.Then, with (0.0125 ") size, and at 275 ℃ of following stress relief annealings 2 hours, measurement performance under this condition, the result is as shown in table 5 under the alloy cold rolling 50% to 0.32mm.
Data in the table 5 show: although base alloy J477 can provide the superperformance combination of 634MPa (92ksi) YS and 58.1%IACS electroconductibility, but, the interpolation of Fe can increase to the intensity of base alloy 690MPa (100ksi) (the relative J477 of J483), and electroconductibility only has decline slightly.And, by comparing alloy J491 and J481, show that when Ti and Fe content were constant, interpolation Mg can improve this advantage of stress relaxation drag under 105 ℃ when keeping Ni.By comparing the performance of alloy J491 (table 5) and table 2 interalloy J345 and J346, also can find the advantage of Mg.
Embodiment 4
According to technology as shown in Figure 2, the alloy in the table 4 is machined to final dimension, but the not solution heat treatment in the adopting process process.Remove after the zone of oxidation through finishing and grinding, the alloy of described hot rolling attitude be cold-rolled to 0.050 ", and carry out the aging anneal first time, the annealed temperature and time is as shown in table 6, can make the electroconductibility maximum effectively.Then, with under the alloy cold rolling 50% to 0.025 " size, and carry out the aging anneal second time, selected annealing temperature and time are as shown in table 6, select described annealing temperature and time so that excessively do not make the electroconductibility maximum under the remollescent situation at matrix.Table 6 shows the concrete aging anneal technology that every kind of alloy adopts.Then, with under the alloy cold rolling 50% to 0.0125 " size, and at 275 ℃ of following stress relief annealings 2 hours, measurement performance under this condition, the result is as shown in table 7.Use this technology, the alloy that adds Fe and Mg provides lower but still good intensity and the electroconductibility of Geng Gao and good stress relaxation drag.
Embodiment 5
Adopt method shown in Figure 3, melting and employing Durville casting cast out a series of 4.5kg (10 pounds) laboratory ingot castings of analyzing composition shown in the table 8 that have in punching block in quartz crucible.After cast, ingot casting is of a size of 10.16cmx10.16cmx4.45cm (4 " X4 " X1.75 ").After 950 ℃ were incubated 3 hours down, (1.1 ") were thick, reheat 10 minutes under 950 ℃, and (0.50 ") size afterwards, is carried out shrend to adopt 3 passages further to be hot-rolled down to 1.27cm to adopt 3 passages that ingot casting is hot-rolled down to 2.8cm.Remove after the zone of oxidation through finishing and grinding, alloy is cold-rolled to 2.54mm, and (0.100 ") is thick, and solution heat treatment 40 seconds in 950 ℃ stove, afterwards, carries out shrend, with the controlled tiny recrystallization crystal particle dimension of acquisition 8-12 μ m.Afterwards, with (0.050 ") size, and 565 ℃ of following aging anneals 3 hours, purpose was excessively not make the electroconductibility maximum under the remollescent situation at matrix under the alloy cold rolling 50% to 1.27mm.Then, with under the alloy cold rolling 50% to 0.64mm (0.025 ") size, and, under 410 ℃, carry out 2 hours the aging anneal second time, be cold-rolled to 0.25mm (0.010 ").Subsequently, 250 ℃ of following stress relief annealings 2 hours.Measurement performance under this condition, the result is as shown in table 9.
Contrast benchmark alloy J694 and contain zirconium alloy J698, confirm: a spot of zirconium can improve yield strength under the situation that does not influence electroconductibility.Comparative alloy J694 with contain silver alloys J699, confirm: a spot of silver can improve yield strength and electroconductibility simultaneously.Reference alloys J694 and chrome-bearing alloy J700, confirm: a spot of chromium can improve yield strength slightly under the situation that electroconductibility reduces slightly.
Embodiment 6
Adopt method shown in Figure 3, melting and employing Durville casting cast out a series of 4.5kg (10 pounds) laboratory ingot castings of analyzing composition shown in the table 10 that have in punching block in quartz crucible.After cast, ingot casting is of a size of 10.16cmx10.16cmx4.45cm (4 " X4 " X1.75 ").After 950 ℃ were incubated 3 hours down, (1.1 ") were thick, reheat 10 minutes under 950 ℃, and (0.50 ") size afterwards, is carried out shrend to adopt 3 passages further to be hot-rolled down to 1.27cm to adopt 3 passages that ingot casting is hot-rolled down to 2.8cm.Remove after the zone of oxidation through finishing and grinding, with alloy be cold-rolled to 2.54mm (0.100 "), and in 1000 ℃ stove solution heat treatment 25-35 second, afterwards, carry out shrend, with the controlled tiny recrystallization crystal particle dimension of acquisition 6-12 μ m.Afterwards, with (0.050 ") size, and under the alloy cold rolling 50% to 1.27mm at 550-600 ℃ of following aging anneal 3-4 hour.Then, with under the alloy cold rolling 50% to 0.64mm (0.025 ") size, and, under 410-425 ℃, carry out 2 hours aging anneal once more, subsequently, be cold-rolled to 0.25mm (0.010 "), and, 250-275 ℃ of following stress relief annealing 2 hours.
Performance when table 11 shows final dimension shows: add Mg (J604 compares with J603) and/or add Zr (J644 compares with J603), can obtain the combination of better yield strength and electroconductibility.
If do not add Mg, then add Cr effect relatively poor (higher-strength than J700 in low strength and the table 9 of J646 in the table 11 (D row) is compared) separately.Be also shown in by table 11 in the content range of following Mg, how the interpolation of Mg improves yield strength (and tensile strength), wherein works as the Mg addition and is respectively 0,0.16,0.25, during 0.31wt%, its yield strength (and tensile strength) is respectively 703 (758), and 710 (772), 745 (772), 745 (800), 758 (814) MPa[102 (110), 103 (112), 108 (116), 110 (118) ksi], and simultaneously electroconductibility almost is maintained at about 48%IACS and invariable.
Embodiment 7
What this embodiment illustrated is how composition and technology influence yield strength and electroconductibility.(ingot casting of 4 " x4 " x 1.75 ") carries out following processing and obtains to form alloy J694 as shown in table 12 and J709:950 ℃ insulation 3 hours down, is hot-rolled down to 1.27cm (0.50 inch), afterwards, carries out shrend to being of a size of 10.16cmx10.16cmx4.45cm.Remove after the zone of oxidation through finishing and grinding, alloy is cold-rolled to 2.54mm (0.10 "), and 1000 ℃ of following solution heat treatment 35 seconds, afterwards, carry out shrend.Then, (0.050 ") is 950 ℃ of following solution treatment 35 seconds and carry out shrend alloy to be cold-rolled to 1.27mm.Further treatment process is as shown in table 13, and performance then provides in table 14.
Table 12
| Alloy | Form |
| J694 | Cu-1.78Ni-1.34Ti-0.98Fe-0.24Mg |
| Alloy | Form |
| J709 | Cu-0.93Ni-0.90Ti-1.05Fe-0.24Mg |
Table 13
| Technology | From the later processing step of 1.27mm (0.05 inch) |
| J1 | 565 ℃ of down annealing 3 hours+be cold-rolled to 0.64mm (0.025 inch)+410 ℃ annealing 2 hours down+be cold-rolled to 0.38mm (0.015 inch)+250 ℃ annealing 2 hours down |
| J2 | 0.008 inch+250 ℃ of 0.025 inch+410 ℃ of 565 ℃ of down annealing 3 hours+be cold-rolled to annealing 2 hours down+be cold-rolled to annealing 2 hours down |
Table 14
The front is introduced one or more embodiments of the present invention.It should be understood, however, that as long as without departing from the spirit and scope of the present invention, can carry out various changes.Therefore, other embodiment all is in the scope of back claim.
Claims (15)
1. copper base alloy, it basic composition is, by weight: 0.35-5% titanium, 0.001-10% are selected from Ni, Fe, Co, Mg, Cr, Zr, the rest is copper and unavoidable impurities at one or more elements of Ag and their combination, the electroconductibility of described alloy is 50%IACS at least, and yield strength is 724MPa at least.
2. according to the copper base alloy of claim 1, it contains and is selected from one or more following elements: maximum 5.0% Ni, maximum 1.10% Fe, Co or their mixture, maximum 1.0% Mg, maximum 1% one or more be selected from the element of Cr, Zr and Ag.
3. according to the copper base alloy of claim 2, also contain in its essentially consist: 0.35-2.5% titanium, 0.5-5.0% nickel; 0.5-0.8% iron, cobalt or their mixture; 0.01-1.0% magnesium; Maximum 1% Cr, Zr, Ag or its combination; The rest is copper and unavoidable impurities.
4. according to the copper base alloy of claim 2, its essentially consist also contains: the 0.8-1.4% titanium; 0.8-1.7% nickel; 0.9-1.1% iron, cobalt or their mixture; 0.1-0.4% magnesium; Maximum 1% Cr, Zr, Ag or its combination; The rest is copper and unavoidable impurities.
5. the copper base alloy of the yield strength with improvement, electroconductibility and the combination of stress relaxation drag, it basic composition is, by weight: the 0.35-2.5% titanium; 0.5-5.0% nickel; 0.5-1.5% iron, cobalt or their mixture; 0.01-1.0% magnesium; Maximum 1% Sn, Cr, Zr, Ag, Sn, P, Al, Si, Pb, Bi, S, Te, Se, Be, Mn, As, Sb, B or their mixture; The rest is copper and unavoidable impurities.
6. according to the copper base alloy of claim 5, it contains maximum 1% Cr, Zr, Ag or their mixture.
7. according to the copper base alloy of claim 6, it basic composition is: the 0.8-1.4% titanium; 0.8-1.7% nickel; 0.90-1.10% iron, cobalt or their mixture; 0.10-0.40% magnesium; The Cr of 0.01-1.0%, Zr, Ag or their mixture; The rest is copper and unavoidable impurities.
8. the preparation method of the copper base alloy of the yield strength with improvement, electroconductibility and the combination of stress relaxation drag, it is characterized in that: casting (10) copper base alloy, described alloy basic composition is, by weight: 0.35-10% titanium, 0.001-6% are selected from Ni, Fe, Co, Mg, Cr, the rest is copper and unavoidable impurities at one or more elements among Zr and the Ag; At the described alloy of 750-1000 ℃ of following hot rolling (12); Depress the described alloy of comparison with the area of 50-97% and carry out the first time cold rolling (14); Under 850-1000 ℃ described alloy is carried out the annealing first time (16), the time, afterwards, cooling (18) was to room temperature fast from 10 seconds to 1 hour; Depress the described alloy of comparison and carry out the second time cold rolling (20) to be up to 80% area; Under 400-650 ℃ described alloy is carried out the annealing second time (22), the time was from 1 minute to 10 hours; With the area of 10-50% depress than with described alloy cold rolling for the third time (24) to final dimension, the time of wherein said each annealing steps and temperature effectively make the described alloy of final dimension have the yield strength of 724MPa at least and the electroconductibility of 50%IACS at least.
9. method according to Claim 8, it is characterized in that: at described cold rolling step for the third time (24) afterwards, under 150-600 ℃ described alloy is annealed (26), the time was from 15 seconds to 10 hours.
10. yield strength, electroconductibility and combination of stress relaxation drag with improvement, has simultaneously the preparation method of the copper base alloy of suitable bendability again, it is characterized in that: casting (10) copper base alloy, basic composition is of described alloy, by weight: 0.35-10% titanium, 0.001-6% are selected from Ni, Fe, Co, Mg, Cr, the rest is copper and unavoidable impurities at one or more elements among Zr and the Ag; (12) described alloy under 750-1000 ℃ of following hot pressing; Implement one or more circulations, described circulation comprises with the area of 50-99% depresses than colding pressing following (14) described alloy and carry out aging anneal (28) from 15 seconds to 10 hours afterwards under 400-650 ℃ annealing temperature; Depress than (30) the described alloy down of colding pressing with the area of 40-80%; By annealing 1-10 hour down, described alloy is carried out age hardening handle (32) at 400-650 ℃; With the area of 10-50% depress than with described alloy finally cold rolling (34) to final dimension, the time of wherein said annealing steps and temperature effectively make the described alloy of final dimension have the yield strength of 724MPa at least and the electroconductibility of 50%IACS at least.
11. the method according to claim 10 is characterized in that: at described final cold rolling step (34) afterwards, under 150-600 ℃ described alloy is annealed (26), the time was from 15 seconds to 10 hours.
12. preparation method with copper base alloy of high-yield strength and suitable intensity, electroconductibility, it is characterized in that: casting (10) copper base alloy, described alloy basic composition is, by weight: 0.35-10% titanium, 0.001-6% are selected from Ni, Fe, Co, Mg, Cr, the rest is copper and unavoidable impurities at one or more elements among Zr and the Ag; (12) described alloy under 750-1000 ℃ of following hot pressing; Depress than (14) the described alloy down of colding pressing with the area of 50-99%; Under 950-1000 ℃ described alloy is carried out solution annealing (16), the time afterwards, was quickly cooled to envrionment temperature from 15 seconds to 1 hour; Depress than (20) the described alloy down of colding pressing with the area of 40-60%; Under 400-650 ℃ described alloy is carried out aging anneal (28), the time is 1-10 hour; Depress than (30) the described alloy down of colding pressing with the area of 40-60%; Under 375-550 ℃ the ratio temperature that aging anneal is low for the first time, alloy is carried out the aging anneal second time (32), time 1-3 hour; And, to depress than cold rolling (34) to final dimension with at least 30% area, the time of wherein said annealing steps and temperature effectively make the described alloy of final dimension have the yield strength of 724MPa at least and the electroconductibility of 50%IACS at least.
13. the method according to claim 12 is characterized in that: at described final cold rolling step (34) afterwards, under 150-600 ℃ described alloy is annealed (26), the time was from 15 seconds to 10 hours.
14. preparation method with copper base alloy of high-yield strength and suitable intensity, electroconductibility, it is characterized in that: casting (10) copper base alloy, basic composition is of described alloy, by weight: 0.35-10% titanium, 0.001-6% are selected from Ni, Fe, Co, Mg, Cr, the rest is copper and unavoidable impurities at one or more elements of Zr and Ag and their combination; At the described alloy of 750-1000 ℃ of following hot rolling (12); Depress than cold rolling (14) described alloy with the area of 50-99%; Under 950-1000 ℃ described alloy is carried out solution annealing (16), the time, afterwards, cooling (18) was to envrionment temperature fast from 10 seconds to 1 hour; Depress than cold rolling (20) described alloy with the area of 40-60%; Described alloy is carried out aging anneal (28), and annealing temperature is 500-575 ℃, and the time, perhaps, annealing temperature was 425-475 ℃, time 2.5-3.5 hour from 15 seconds to 10 hours; Depress than cold rolling (30) described alloy with the area of 40-60%; Under 500-550 ℃ temperature, alloy is carried out the aging anneal second time (32), time 1-4 hour; And, to depress than finally cold rolling (34) to final dimension with at least 30% area, the time of wherein said annealing steps and temperature effectively make the described alloy of final dimension have the yield strength of 724MPa at least and the electroconductibility of 50%IACS at least.
15. the method according to claim 14 is characterized in that: at described final cold rolling step (34) afterwards, under 150-600 ℃ described alloy is annealed (26), the time was from 15 seconds to 10 hours.
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| US41059202P | 2002-09-13 | 2002-09-13 | |
| US60/410,592 | 2002-09-13 | ||
| PCT/US2003/027856 WO2004024964A2 (en) | 2002-09-13 | 2003-09-05 | Age-hardening copper-base alloy and processing |
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| EP (1) | EP1537249B1 (en) |
| JP (2) | JP4590264B2 (en) |
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- 2003-09-05 JP JP2004536112A patent/JP4590264B2/en not_active Expired - Fee Related
- 2003-09-05 KR KR1020057004299A patent/KR20050050654A/en not_active Application Discontinuation
- 2003-09-05 MX MXPA05002640A patent/MXPA05002640A/en unknown
- 2003-09-05 AU AU2003272276A patent/AU2003272276A1/en not_active Abandoned
- 2003-09-05 US US10/657,005 patent/US20040166017A1/en not_active Abandoned
- 2003-09-05 WO PCT/US2003/027856 patent/WO2004024964A2/en active Application Filing
- 2003-09-05 CA CA002497819A patent/CA2497819A1/en not_active Abandoned
- 2003-09-05 EP EP03754452.5A patent/EP1537249B1/en not_active Expired - Lifetime
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2005539140A (en) | 2005-12-22 |
| EP1537249A2 (en) | 2005-06-08 |
| TW200422410A (en) | 2004-11-01 |
| AU2003272276A1 (en) | 2004-04-30 |
| MXPA05002640A (en) | 2005-07-19 |
| CA2497819A1 (en) | 2004-03-25 |
| KR20050050654A (en) | 2005-05-31 |
| WO2004024964A2 (en) | 2004-03-25 |
| WO2004024964A3 (en) | 2004-07-01 |
| US20040166017A1 (en) | 2004-08-26 |
| JP4590264B2 (en) | 2010-12-01 |
| JP2010275640A (en) | 2010-12-09 |
| EP1537249A4 (en) | 2007-07-11 |
| CN1688732A (en) | 2005-10-26 |
| EP1537249B1 (en) | 2014-12-24 |
| AU2003272276A8 (en) | 2004-04-30 |
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