CN1793394A - Copper alloy having bendability and stress relaxation property - Google Patents
Copper alloy having bendability and stress relaxation property Download PDFInfo
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- CN1793394A CN1793394A CN 200510134104 CN200510134104A CN1793394A CN 1793394 A CN1793394 A CN 1793394A CN 200510134104 CN200510134104 CN 200510134104 CN 200510134104 A CN200510134104 A CN 200510134104A CN 1793394 A CN1793394 A CN 1793394A
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Abstract
A copper alloy contains 0.01% to 1.0% of Fe, 0.01% to 0.4% of P, and 0.1% to 1.0% of Mg with the remainder being copper and inevitable impurities and has a volume fraction of dispersoids having a particle diameter exceeding 200 nm of 5% or less, in which dispersoids having a particle diameter of 200 nm or less and containing Mg and P have an average particle diameter of 5 nm or more and 50 nm or less. The copper alloy preferably has an average particle diameter of dispersoids containing Fe and P of 20 nm or less. The copper alloy has improved bendability and stress relaxation property.
Description
Technical field
The present invention relates to have the copper alloy of bendability and stress relaxation performance.Particularly, it relates to the raw material used at the copper alloy sheet material that semiconductor element for example uses in the IC lead frame of semiconductor device by using of suiting; The electrical/electronic element is the material used of printed-wiring board (PWB) for example; Switching element; With mechanical organ for example bus, terminating unit and junctor.
Background technology
The Cu-Fe-P alloy has been usually used as the copper alloy of the IC lead frame that is used for application examples in the above such as semiconductor device by using.The example of these Cu-Fe-P alloys comprises: contain 0.05% to 0.15% Fe and 0.025% to 0.040% P copper alloy (C19210 alloy) and contain the copper alloy (CDA194 alloy) of the Zn of 2.1% to 2.6% Fe, 0.015% to 0.15% P and 0.05% to 0.20%.In these copper alloys, when disperseing the intermetallic compound of Fe for example or Fe and P in copper matrix, these Cu-Fe-P alloys show high strength, high conductivity and high thermal conductivity, and therefore, these have been usually used as the international standard alloy.
Along with the application that improves day by day, the Cu-Fe-P alloy must have such performance, and to keep in touch adaptive faculty in thermal environment, promptly so-called stress relaxation performance is as the performance of guaranteeing the reliability in thermal environment.Particularly, when when thermal environment is for example placed coupling element in the engine room of automobile, the stress pine is executed, and As time goes on contact pressure reduce, and the contact resistance of joint tends to improve.Therefore, coupling element has lost their contact adaptive faculty.Therefore, " stress relaxation performance " is the resistance of opposing that contact adaptive faculty (stress) reduces.Believe that the stress relaxation performance improves along with the minimizing of stress relaxation rate.
The various technology of stress relaxation performance have been proposed to improve.For example Japanese Patent No.2977839 discloses the copper alloy that a kind of electrical/electronic element is used, it comprises the Zn of P, 0.3 to 1.5 weight % (not comprising 1.5 weight %) of Fe, 0.01 to 0.1 weight % of Sn, 0.02 to 0.50 weight % of 0.1 to 1.0 weight % and the Mg of 0.1 to 1.0 weight %, and wherein surplus is Cu basically.According to this technology, add Fe and P together to form iron phosphide, limit thereby improve elastic force.In addition, copper alloy will have softening resistance, particularly excellent creep property and the stress relaxation performance under the temperature that improves.
The open No.2002-294368 of Japanese unexamined patent has proposed the copper alloy that a kind of terminating unit and junctor are used, it comprises 0.8% to 1.5% Ni, 0.5% to 2.0% Sn, 0.015% to 5.0% Zn and 0.005% to 0.1% P, wherein sedimental area ratio is 5% or lower, opposes the anti-parent phase (suppressing the migration of slip band and the effect that dislocation disappears) of stress relaxation and improves the stress relaxation performance with maintenance.
The Cu-Fe-P alloy that need be used for above-mentioned application has can be guaranteed quirk for example the U type is crooked or the excellent bendability of 90 ℃ of bendings behind fluting, and high strength and high conductivity.
But above-mentioned solid solution hardening element is the adding of Sn and Mg for example, or recently improves the deterioration that intensity causes bendability inevitably by improving cold rolling compression, and therefore, the intensity and the bendability that need can not be compatible.
On the other hand, be known that by grain refining or the state by the control dispersoid and can improve bendability (the open No.2001-279347 of open No.6-235035 of Japanese unexamined patent and Japanese unexamined patent) to a certain extent.But, reduce compatible high strength Cu-Fe-P alloy in order to prepare to have recent years with size of component and weight, become indispensable by improving cold rolling compression ratio raising workpiece hardened quality.
Therefore, as for above-mentioned high-strength material, by disclosed microstructure control example such as grain refining or control dispersoid state in open No.6-23503 of Japanese unexamined patent and the open No.2001-279347 of Japanese unexamined patent, enough for example U-is crooked or 90 ℃ of bendings for the quirk behind the above-mentioned fluting of improvement.
As for the Cu-Fe-P alloy, the open No.2002-339028 of Japanese unexamined patent proposes microstructural control.Particularly, its proposes the volume efficiency of (200) diffraction and (220) diffraction: I (200)/I (220) is 0.5 or higher and 10 or lower, the density of Cube orientation is 1 or higher and 50 or lower, or the ratio of the density of Cube orientation and the density of S orientation is 0.1 or higher and 5 or lower.
The open No.2000-328157 of Japanese unexamined patent has proposed the strength ratio of (200) diffraction and (311) diffraction sum (220) diffraction: [I (200)+I (311)]/I (220) is 0.4 or higher.
Summary of the invention
Routine techniques for example reduces the settling area ratio among the open No.2002-294368 of adjusting alloying component and Japanese unexamined patent in Japanese Patent No.2977839 can not enough improve the stress relaxation performance.These technology can not make alloy have bendability simultaneously.
Microstructural control does not obtain excellent stress relaxation performance among open No.2002-339028 of Japanese unexamined patent and the open No.2000-328157 of Japanese unexamined patent, though the bendability that they are improved.
Therefore, an object of the present invention is to provide a kind of Cu-Fe-P alloy that has with the reconcilable excellent bendability of excellent stress relaxation performance.
In order to reach top purpose, one aspect of the present invention is an Albatra metal-, it has bendability and stress relaxation performance, and comprise the P of Fe, 0.01 to 0.4 quality % of 0.01 to 1.0 quality % and the Mg of 0.1 to 1.0 quality %, wherein surplus is copper and unavoidable impurities, wherein to surpass the volume fraction of the dispersoid of 200nm be 5% or lower to the particle dia separately of copper alloy, and wherein separately particle dia be that 200nm or average particle diameter lower and that contain the dispersoid of Mg and P are 5nm or higher and 50nm or lower.
In order further to improve bendability and stress relaxation performance, preferred particle dia separately is 200nm or lower and to contain the average particle diameter that the dispersoid of Mg and P has be 1nm or higher and 20nm or lower.
In order further to improve bendability and stress relaxation performance, copper alloy can also comprise the Ni of 0.01 to 1.0 quality % and at least one among the Co.
In order to improve that Sn electroplates and scolder heat-resisting ablative, copper alloy can also comprise the Zn of 0.005 to 3.0 quality %, thereby prevents thermal ablation (hot soarfing from).Descend for fear of specific conductivity, preferred Zn content is 0.005 to 1.5 quality %.
In order to improve intensity, copper alloy can also comprise the Sn of 0.01 to 5.0 quality %.Descend for fear of specific conductivity, preferred Sn content is 0.01 to 1.0 quality %.
According to aspects of the present invention, Cu-Fe-P alloy and Mg combination with the intensity with improvement and the stress relaxation performance of improvement, and reduces the coarse dispersoid that particle dia surpasses 200mm.
Particle dia is above the recrystallize in the coarse dispersoid promotion thermal environment of 200mm, thereby reduction stress relaxation performance causes deformation fracture and impels crack propagation, thereby reduces bendability.
In order more effectively to improve bendability and stress relaxation performance by add Mg in the Cu-Fe-P alloy, comprising the average particle diameter that the dispersoid of Mg and P (Mg-P particle) should have is 5nm or higher and 50nm or lower.These fine Mg-P particles prevent moving and grain growing of dislocation, thereby improve bendability and stress relaxation performance expeditiously.
These fine Mg-P particles are at first found by the inventor these role and influence of Cu-Fe-P alloy property.
Term used herein " dispersoid that contains Mg and P " be meant the dispersoid that contains Mg and P, its total content be in the particle total component 60% or higher.Similarly, term " dispersoid that comprises Fe and P " be meant the dispersoid that comprises Fe and P, its total content be in the particle total component 60% or higher.
Embodiment
The composition of copper alloy
To describe the present invention below and be suitable for satisfying needed intensity and electric conductivity, and satisfy the chemical constitution of the Cu-Fe-P alloy of excellent bendability and excellent stress relaxation performance.
In the present invention, as for the essentially consist that reaches high strength, high conductivity, high bendability and heavily stressed relaxation performance, copper alloy comprises the P of Fe, 0.01 to 0.4 quality % of 0.01 to 1.0 quality % and the Mg of 0.1 to 1.0 quality %, and wherein surplus is copper and unavoidable impurities.
In another embodiment, with respect to this essentially consist, also comprise at least one among the Ni of following scope and at least one and/or Zn and the Sn among the Co.Can comprise other impurity element, its scope is not for weakening these performances.
(Fe)
It is 200nm or lower Fe or Fe-P dispersoid that iron (Fe) is deposited as particle dia, and is a kind of important element, and it improves the intensity and the stress relaxation performance of copper alloy.If the content of Fe is lower than 0.01 quality %, the generation of above-mentioned trickle dispersoid is little.The content of Fe should be 0.01 quality % or higher, more effectively to show these advantages.On the other hand, if the content of Fe surpasses 1.0 quality %, dispersoid is grown and is become coarse, so intensity, bendability and stress relaxation performance are lowered.Therefore, regulation Fe content is in 0.01 to 1.0 quality % scope.
(P)
Phosphorus (P) is realized deoxidation, is that a kind of and Fe and/or Mg form the important element that particle dia is 200nm or lower trickle dispersoid in addition, thereby improves the intensity and the stress relaxation performance of copper alloy.If P content is lower than 0.01 quality %, can not fully form trickle dispersoid.P content must be 0.01 quality % or higher, with for example improvement of stress relaxation performance of effective display effect.On the other hand, if P content surpasses 0.4 quality %, dispersoid is grown and is become coarse, so bendability, stress relaxation performance and hot workability are lowered.Therefore, regulation Fe content is in 0.01 to 0.4 quality % scope.
(Mg)
Magnesium (Mg) is a kind ofly to form the important element that particle dia is 200nm or lower trickle dispersoid with P in copper alloy, thereby improves intensity and stress relaxation performance.If P content is lower than 0.1 quality %, can not fully form trickle dispersoid.Therefore, Mg content must be 0.1 quality % or higher, with these effects of effective demonstration.On the other hand, if Mg content surpasses 1.0 quality %, dispersoid is grown and is become coarse, is lowered so reduce intensity, bendability and stress relaxation performance.Therefore, regulation Mg content is in 0.1 to 1.0 quality % scope.
(Ni、Co)
Copper alloy can also comprise at least a among the Ni of 0.01 to 1.0 quality % and the Co.Nickel (Ni) and cobalt (Co), generally with Fe, as the trickle dispersoid deposition in the copper alloy, for example the trickle dispersoid of (Ni, Co)-P or (Ni, Co)-Fe-P deposits, to improve intensity and stress relaxation performance.The total content of Ni and Co is necessary for 0.01 quality % or higher, with these effects of effective demonstration.On the contrary, if the total content of Ni and Co surpasses 1.0 quality %, it is coarse that dispersoid becomes, so intensity, bendability and stress relaxation performance are lowered.Therefore, the total content of regulation Ni and Co is in 0.01 to 1.0 quality % scope.
(Zn)
Copper alloy can also comprise at least a among Zn and the Sn.Zinc (Zn) be a kind of be used to improve heat-resisting ablative and be used to prevent that Sn that the electronic component joint is used from electroplating and the effective element of the thermal ablation of scolder.The content of preferred Zn is 0.005 quality % or higher, with these effects of effective demonstration.On the contrary, too high Zn content has reduced the wetting properties and the diffustivity of fusion Sn and scolder, in addition, greatly reduces electric conductivity.Therefore, optionally comprise Zn, its content is 0.005 to 3.0 quality %, is preferably 0.005 to 1.5 quality %, and is heat-resisting ablative and to avoid the reduction of electric conductivity to improve.
(Sn)
Tin (Sn) is dissolved in the improvement that the copper alloy neutralization helps intensity.Preferred Sn content is 0.01 quality % or higher, with these effects of effective demonstration.On the other hand, if Sn content is too high, its effect is saturated.On the contrary, electric conductivity reduces greatly.Consider this point, optionally comprise Sn, its content is 0.01 to 5.0 quality %, and is preferably 0.01 to 1.0 quality %.
(other element)
Other element is impurity basically, and preferably minimized.For example, impurity element for example Al, Cr, Ti, Be, V, Nb, Mo and W makes dispersoid become coarse usually, and causes that electric conductivity descends.Therefore, preferably with the minimum 0.5 quality % or lower that turns to of the total content of these elements.Other minor element in copper alloy for example B, C, Na, S, Ca, As, Se, Cd, In, Sb, Pb, Bi and MM (norium) may cause the decline of electric conductivity.Therefore, preferably with the minimum 0.1 quality % or lower that turns to of the total content of these elements.
More specifically, preferably the total content of (1) Mn, Ca, Zr, Ag, Cr, Cd, Be, Ti, Co, Ni, Au and Pt is that 1.0 quality % or total content lower and (2) Hf, Th, Li, Na, K, Sr, Pd, W, S, Si, C, Nb, Al, V, Y, Mo, Pb, In, Ga, Ge, As, Sb, Bi, Te, B and norium are 0.1 quality % or lower.
(dispersoid distribution)
Then, the following defined of the distribution of the dispersoid in the copper alloy is to reach heavily stressed relaxation performance and high bendability.
(coarse dispersoid)
Particle dia is that the coarse dispersoid of 200nm promotes the recrystallize in the thermal environment in copper alloy, thereby reduces the stress relaxation performance, causes deformation fracture and impels crack propagation, thereby reduce bendability, and have nothing to do with its composition.Therefore, the volume fraction that particle dia in the copper alloy should be surpassed the coarse dispersoid of 200nm is minimised as 5 quality % or lower, and no matter the composition of dispersoid.
(Mg-P particle)
At particle dia is in 200nm or the lower dispersoid, and it is 5nm or higher and 50nm or lower that regulation comprises the particle dia that those dispersoids (Mg-P particle) of Mg and P have.These trickle Mg-P particles help to suppress the improvement of dislocation moving and grain growing and bendability and stress relaxation performance very much.
According to the present invention, the Mg-P particle that particle dia is surpassed 200nm minimizes, and the regulation particle dia is that 200nm or lower Mg-P particle have the average particle diameter of stipulating above.In the calculating of average particle diameter, do not comprise that particle dia surpasses the Mg-P particle of 200nm.This is because particle dia should be surpassed the Mg-P particle of 200nm minimizes, and should increase the trickle Mg-P particle that helps to improve very much bendability and stress relaxation performance.
Surpass 50nm if particle dia is 200nm or average particle diameter lower and that contain the dispersoid of Mg and P, effectively do not suppress dislocation moving and grain growing so.Thereby, the regulation mainly contain Mg and P dispersoid average particle diameter on be limited to 50nm.On the contrary, be lower than 5nm if contain the average particle diameter of the dispersoid of Mg and P, particle does not help to suppress dislocation moving and grain growing effectively, and can not improve stress relaxation performance and bendability.Therefore, regulation mainly contains the following 5nm of being limited to of average particle diameter of the dispersoid of Mg and P.
(Fe-P particle)
At particle dia is in 200nm or the lower dispersoid, and particle dia is that 1 to 20nm the dispersoid that mainly contains Mg and P (Fe-P particle) shows the pinning force more much higher than coarse dispersoid for suppressing dislocation moving and disappearing.Therefore, in order further to improve bendability and stress relaxation performance, the preferred particle diameter is that 200nm or the lower and average particle diameter of dispersoid that contains Mg and P are in 1nm or higher and 20nm or lower scope.
When copper alloy also comprised among Ni and the Co at least one, these elements formed the dispersoid that contains Ni and/or Co in copper alloy, for example (Ni, Co)-P and (Ni, Co)-Fe-P particle.In order further to improve bendability and stress relaxation performance, as in the Fe-P particle, the average particle diameter that preferably contains the dispersoid of Ni and/or Co is 1nm or higher and 20nm or lower.
But the Ni/Co dispersoid that contains Fe for example (Ni, Co)-Fe-P particle is comprised as used herein in " Fe-P particle " basically.If exist except the Fe-P particle, to contain Ni and/or Co dispersoid, (Ni, Co)-P particle for example, they can be owing to typically passing through the described preferred production process refining in back Fe-P particle by refining so.Therefore,, also do not stipulate and determine to contain the dispersoid of Ni and/or Co even when copper alloy also comprises among Ni and the Co at least one, and as representative regulation Fe-P particle.
In the present invention, the Fe-P particle that particle dia is surpassed 200nm minimizes, and the regulation particle dia is in the described in the above scope of average particle diameter of 200nm or lower Fe-P particle.In the calculating of average particle diameter, do not comprise that particle dia surpasses the Fe-P particle of 200nm.This is because as in the Mg-P particle, should preferably increase the Fe-P particle that helps to improve very much bendability and stress relaxation performance.
Surpass 20nm if mainly contain the average particle diameter of the dispersoid of Fe and P, then pinning force descends.Therefore, preferably mainly contain Fe and P dispersoid average particle diameter on be limited to 20nm.
On the contrary, be lower than 1nm,, and may have low pinning force even use transmission electron microscope under 100000 times magnification, also can not detect and definite this particle if mainly contain the average particle diameter of the dispersoid of Fe and P.Thereby, preferably mainly contain the following 1nm of being limited to of average particle diameter of the dispersoid of Fe and P.
For example, in the production of copper alloy, in the cold rolling after annealing, form these trickle Mg-P particles and trickle Fe-P particle (dispersoid).Particularly, these trickle dispersoids are as annealing result trickle sedimentary compound phase (compound phase) from parent phase.
Therefore trickle dispersoid be different from form by casting and be present in coarse dispersoid in the copper alloy.For example, under 100000 times or higher magnification, can only observe this trickle dispersoid in the copper alloy with transmission electron microscope.
In other words, by under 100000 times magnification, observing copper alloy with transmission electron microscope, can discern that to contain Fe and P and average particle diameter be 1nm or higher and 20nm or these lower dispersoids, and to contain Mg and P and average particle diameter be 5nm or higher and 50nm or lower dispersoid.It is 60% or higher Mg of total component and Mg-P particle and other particle of P that this observation can be distinguished each self-contained total content, it is 60% or higher Fe of total component and Fe-P particle and other particle of P that difference contains total content, and can discern the dispersoid that contains Ni and/or Co.
(TEM) observes microstructure under 100000 times magnification by transmission electron microscope, determines that in the following method particle dia separately is 200nm or the lower Mg-P particle and the average particle diameter of Fe-P particle.At first, measure wide (the 1 μ m of the long 1 μ m of 1 μ m
2) the maximum diameter of dispersoid separately in the microstructure in the visual field is as the particle diameter d of dispersoid separately.
Then, determine that all these particle diameter d surpass the total area ratio of the dispersoid of 200nm.Definition total area ratio among the present invention separately the particle dia that has of dispersoid surpass the volume fraction of the dispersoid of 200nm.
The total content of Fe and P be 60% or the total content of higher Fe-P particle and Mg and P be 60% or higher Mg-P particle be to distinguish in the following method based on the total content of Fe and P with based on the total content of Mg and P respectively.Wherein by using electronic probe X-line trace analysis (electron prove X-raymicroanalysis) energy dispersion X-linear light spectroscopy (EDX) (EPMA) to carry out semi-quantitative analysis.This technology is generally used for analyzing microstructure.Therefore, determine the total content of Mg and P in each dispersoid, and the total content of Fe and P.To contain 60% or the particle of higher Fe and P and contain 60% or higher Mg and the particle of P confirm as Fe-P particle and Mg-P particle respectively.
Determine that particle diameter d separately is each a maximum diameter of 200nm or lower Fe-P particle and Mg-P particle.Average largest diameter then.Therefore, determine that particle dia separately is each a average particle diameter of 200nm or lower Fe-P particle or Mg-P particle.
(preparation condition)
The preferred preparation condition of the copper alloy of coordinating mutually with above-mentioned microstructure that describes below that preparation stipulates according to the present invention.Copper alloy of the present invention is the copper alloy sheet material basically, and also comprises in copper alloy of the present invention: by cutting the rectangular of this sheet preparation at horizontal direction and by sheet material or the rectangular coiled material of making.Except the above-mentioned microstructural cold rolling and annealed optimum condition that is used to reach according to the present invention regulation, by with the usual method same procedure, can prepare copper alloy of the present invention.Therefore, preparation method itself does not need significant variation usually.
That is, cast copper alloy melt, described copper alloy melt have been conditioned and have had above-mentioned preferred chemical constitution.The ingot casting that obtains is carried out shaving (facing), and heating or uniform heating treatment.Carry out hot rolling thereafter.
In order to prevent that particle dia preferably carries out shrend above the formation of the coarse dispersoid of 200nm after hot rolling is finished at elevated temperatures.
Then, carry out cold rolling and annealing, obtain having and need the copper alloy of thickness sheet material, as product.
For Mg-P particle among the present invention and Fe-P dispersion of particles body are controlled within the limits prescribed, it is effective annealing under the condition below.Trickle dispersoid wherein is because annealing new sedimentary compound phase from parent phase.In order to deposit these trickle dispersoids, in the preparation copper alloy, after the hot rolling, carry out cold rolling, annealing then.
But, if only improve the deposition of dispersoid by once annealing, then necessary rising annealing temperature, and this high temperature annealing causes dispersoid growth and coarse.Therefore, Mg-P particle and Fe-P particle may have the too big particle dia that surpasses top specialized range.
Therefore, preferably repeatedly anneal, control simultaneously separately that therefore the annealing temperature of process be 430 ℃ or lower, obtain needing sedimentary dispersoid, and prevented the growth of dispersoid, thereby obtain trickle dispersoid.If annealing time (hold-time) is undue long, dispersoid may grow and become coarse so.Therefore, best annealing time preferably is set.
In addition, preferably carry out between number of times cold rolling in these annealing.The cold rolling lattice imperfection that increased, it plays a part deposition nuclear and helps trickle dispersoid in the annealing of following formation.
Consider these conditions, the preferably hot rolling in copper alloy preparation and carry out twice cold-rolled process and twice annealing process between cold rolling at last, thus obtain having the trickle dispersoid of last surface construction.
Embodiment
By further illustrated in greater detail explanation the present invention with reference to some following EXPERIMENTAL EXAMPLE.Particularly, prepare series of thin copper alloy sheet material by a kind of like this method, this method comprises: under the annealing conditions (temperature and time) that changes, carry out cold rolling and annealing each twice (hot rolling-cold rolling-annealing-cold rolling-second annealing first-cold rolling at last) with the composition that changes.The performance of assessing these copper alloy sheet materials is hardness, electric conductivity and bendability for example.
Particularly, in coreless induction furnace, every Albatra metal-that fusing has the chemical constitution shown in the table 1 carries out ingot casting by semi-continuous casting method and makes, and obtains the ingot casting that 70mm is thick, 200mm is wide and 500mm is long.Shaving is carried out on surface to every kind of ingot casting, then, and heating.After this, carry out hot rolling, with preparation 16mm thick sheet material, and the sheet material that obtains at the quenching-in water of 650 ℃ or higher temperature.Remove the scale of oxidation, after this, carry out cold rolling first (intermediate rolling).The sheet material that obtains is carried out shaving, after this, anneal first with cold rolling.Then, carry out second annealing and cold rolling at last, carry out stress relief annealing then at low temperatures, thereby obtain the copper alloy sheet material of thickness for about 0.2mm.
In the every Albatra metal-shown in the table 1, the surplus of the composition except table 1 descriptive element is Cu.Other element is that the total content of Al, Cr, Ti, Be, V, Nb, Mo and W is 0.1 quality % or lower.The impurity element for example total content of B, C, Na, S, Ca, As, Se, Cd, In, Sb, Pb, Bi and MM (norium) also is 0.1 quality % or lower.
Each annealed temperature and time (℃ * hour) is shown in Table 1.
In each embodiment, from thus the preparation the copper alloy sheet material on cutting sample, and, determine in the microstructure that volume fraction (%), particle dia that particle dia separately surpasses the dispersoid of 200nm are 200nm or lower and to contain the average particle diameter (nm) of the dispersoid of Mg and P and particle dia be 200nm or lower and comprise the average particle diameter (nm) of the dispersoid of Fe and P by top method.The results are shown in the table 2.
Dividually, cutting sample from the copper alloy sheet material of preparation is thus measured hardness and electric conductivity, and is carried out pliability test and stress relaxation performance test.The result also is shown in Table 2.
(measurement of hardness)
By applying the 0.5kg load, carry out the hardness measurement of copper alloy sheet material sample with miniature Vickers hardness tester at four points, and its mean value is taken as hardness.
(measurement of electric conductivity)
By annular knurl, copper alloy sheet material sample is processed into slide plate shape (slip-shaped) test film that 10mm is wide and 30mm is long, use doube bridge resistance instrument measuring resistance, and calculate electric conductivity with average area of section method.
(assessment of bendability)
Carry out the pliability test of copper alloy sheet material sample according to Japan Copper and Brass Association Standard.Take out the test film that 10mm is wide and 30mm grows from every kind of sample, carry out GoodWay bending (bending axis is vertical with rolling direction), whether the existence of usefulness opticmicroscope visual observation curved part crackle under 50 times magnification.According to following criterion evaluation bendability: good: there is not crackle, general: slight crackle, failure: obvious crackle.
(proof stress relaxation property)
Every kind of test film is heated and kept 1000 hours at 150 ℃, according to the stress relaxation performance of Electronics MaterialsManufacturers Association of Japan Standard (EMAS-3003) evaluation test sheet.Particularly, the one side of the test film after keeping heating determines that 0.2% the stress of yielding stress under 80% load is initial stress.Determine stress relaxation rate (%) according to following equation: stress relaxation rate (%)={ [(the test film stress after the heating)-(the test film stress before the heating)]/(the test film stress before the heating) } * 100.When high temperature under the constant strain keeps long-time, carry out this test, typically to determine the STRESS VARIATION of terminal (terminal).The alloy that will have under-relaxation rate more is evaluated as the alloy with high more proof stress relaxation property.Assess the stress relaxation performance parallel with rolling direction.
Table 1 shows: invention sample 1 to 13 is the copper alloys with the composition that satisfies requirement of the present invention, and prepares under optimum condition, wherein carry out cold rolling and annealing each twice, and each annealing temperature is set to 430 ℃ or lower.
The volume fraction that invention sample 1 to 13 particle dia separately surpasses the dispersoid of 200nm is 5% or lower, the average particle diameter that wherein contains the dispersoid of Mg and P is 5nm or higher and 50nm or lower, and the average particle diameter that contains the dispersoid of Fe and P is 1nm or higher and 20nm or lower.Back parameter here is preferred requirement.
Thereby invention sample 1 to 13 has high strength and high conductivity, and its yielding stress is 400MPa or higher, and hardness is that 135Hv or higher and electric conductivity are 60%IACS or higher, and has excellent bendability and stress relaxation performance.
On the contrary, the Fe content of the copper alloy of comparative sample 14 is lower than the lower limit of 0.01 quality %.This Albatra metal-has Mg and the P content that satisfies requirement of the present invention, and is to prepare comprising under the optimum condition of annealing temperature.Therefore, it has the average particle diameter of the dispersoid that contains Mg and P that satisfies requirement of the present invention, therefore has excellent bendability and stress relaxation performance, but has low strength.It fails to reach high strength and high conductivity.
The Fe content of the copper alloy of comparative sample 15 surpasses the upper limit of 1.0 quality %.This copper alloy has Mg and the P content that satisfies requirement of the present invention, and is to prepare under the optimum condition that is comprising annealing temperature.Therefore, it has the average particle diameter of the dispersoid that contains Mg and P that satisfies requirement of the present invention, surpasses 5% but its particle dia surpasses the volume fraction of the dispersoid of 200nm, thereby not only shows low strength, and show low bendability and low-stress relaxation performance.
The P content of the copper alloy of comparative sample 16 is lower than the lower limit of 0.01 quality %.This Albatra metal-is to prepare comprising under the optimum condition of annealing temperature, therefore, has the average particle diameter of the dispersoid that contains Mg and P that satisfies requirement of the present invention.But it has low-stress relaxation performance, because P contains the absolute magnitude deficiency that quantity not sufficient causes the trickle dispersoid that contains Mg and P.
The P content of the copper alloy of comparative sample 17 surpasses the upper limit of 0.4 quality %.Though this Albatra metal-is to prepare comprising under the optimum condition of annealing temperature, it contains the coarse dispersoid that contains Mg and P that average particle diameter surpasses the upper limit.In addition, this alloy is owing to the dissolved formation sosoloid of excessive P has significantly low electric conductivity, and its intensity, bendability and stress relaxation performance are low.
The Mg content of the copper alloy of comparative sample 18 is lower than the lower limit of 0.1 quality %.This Albatra metal-is to prepare comprising under the optimum condition of annealing temperature, therefore, has the average particle diameter of the dispersoid that contains Mg and P that satisfies requirement of the present invention.But because contain the absolute magnitude deficiency of the trickle dispersoid of Mg and P, it has low bendability and low stress relaxation performance.
The Mg content of the copper alloy of comparative sample 19 surpasses the upper limit of 1.0 quality %.Though this Albatra metal-is to prepare comprising under the optimum condition of annealing temperature, but it contains the coarse dispersoid that contains Mg and P that average particle diameter surpasses the upper limit, the volume fraction that its particle dia surpasses the dispersoid of 200nm surpasses 5%, therefore, its low strength, bendability and stress relaxation performance are low.
The copper alloy of comparative sample 20 has the composition in the specialized range of the present invention, and it is annealing first above under 430 ℃ the too high annealing temperature, though the second annealing temperature is lower than 430 ℃.The copper alloy that obtains comprises: average particle diameter surpasses the coarse dispersoid that contains Mg and P of the upper limit and contains the coarse dispersoid of Fe and P separately, and the volume fraction that its particle dia surpasses the dispersoid of 200nm surpasses 5%.Therefore, its intensity, low bendability and low-stress relaxation performance are low.
The copper alloy of comparative sample 21 has the composition in the specialized range of the present invention, it is annealed first in the undue long time, though temperature wherein is lower than 430 ℃.The copper alloy that obtains comprises: average particle diameter surpasses the coarse dispersoid that contains Mg and P of the upper limit and contains the coarse dispersoid of Fe and P separately, and the volume fraction that its particle dia surpasses the dispersoid of 200nm surpasses 5%.Therefore, its intensity, low bendability and low-stress relaxation performance are low.
The copper alloy of comparative sample 22 has the composition in the specialized range of the present invention, but it is annealed first in too low temperature.Therefore, owing to contain the trickle dispersoid of Mg and P and contain the absolute magnitude deficiency of the trickle dispersoid of Fe and P, copper alloy not only electric conductivity is low, and bendability and stress relaxation performance are also low.
The copper alloy of comparative sample 23 has the composition in the specialized range of the present invention, though annealing temperature is lower than 430 ℃ first, it is carrying out second annealing above under 430 ℃ the too high annealing temperature.The copper alloy that obtains comprises: average particle diameter surpasses the coarse dispersoid that contains Mg and P of the upper limit and contains the coarse dispersoid of Fe and P separately, and the volume fraction that its particle dia surpasses the dispersoid of 200nm surpasses 5%.Therefore, its intensity, low bendability and low-stress relaxation performance are low.
The copper alloy of comparative sample 24 has the composition in the specialized range of the present invention, and it carries out second annealing in the undue long time, though temperature wherein is lower than 430 ℃.The copper alloy that obtains comprises: average particle diameter surpasses the coarse dispersoid that contains Mg and P of the upper limit and contains the coarse dispersoid of Fe and P separately, and the volume fraction that its particle dia surpasses the dispersoid of 200nm surpasses 5%.Therefore, its intensity, low bendability and low-stress relaxation performance are low.
The copper alloy of comparative sample 25 has the composition in the specialized range of the present invention, but it carries out second annealing in too low temperature.Therefore, owing to contain the trickle dispersoid of Mg and P and contain the absolute magnitude deficiency of the trickle dispersoid of Fe and P, copper alloy not only electric conductivity is low, and bendability and stress relaxation performance are also low.
When cold rolling and annealing are respectively carried out once, and annealing temperature is when surpassing 430 ℃, and annealing time is too long, or annealing temperature is when too low, and the result is similar in the comparative sample 20 to 25 those.
These results conclusive evidence: the key of copper alloy of the present invention form and golden dispersoid for reaching high strength, high conductivity and the bendability of excellence and the meaning of excellent stress relaxation performance, and the preferred preparation condition is for the meaning that reaches the requirement in the dispersoid.
Table 1
| Situation | Alloy number | The chemical composition of copper alloy sheet material (surplus: Cu and impurity) | Annealing first (℃ * hr) | Second annealing (℃ * hr) | ||||||
| Fe | P | Mg | Ni | Co | Zn | Sn | ||||
| The invention sample | 1 | 0.15 | 0.10 | 0.25 | - | - | - | - | 380×5 | 380×5 |
| 2 | 0.02 | 0.10 | 0.25 | - | - | - | - | 380×5 | 380×5 | |
| 3 | 0.91 | 0.10 | 0.25 | - | - | - | - | 380×5 | 380×5 | |
| 4 | 0.15 | 0.02 | 0.25 | - | - | - | - | 380×5 | 380×5 | |
| 5 | 0.15 | 0.36 | 0.25 | - | - | - | - | 380×5 | 380×5 | |
| 6 | 0.15 | 0.10 | 0.10 | - | - | - | - | 380×5 | 380×5 | |
| 7 | 0.15 | 0.10 | 0.92 | - | - | - | - | 380×5 | 380×5 | |
| 8 | 0.15 | 0.10 | 0.25 | - | - | 0.4 | - | 380×5 | 380×5 | |
| 9 | 0.15 | 0.10 | 0.25 | - | - | - | 0.4 | 380×5 | 380×5 | |
| 10 | 0.15 | 0.10 | 0.25 | - | - | 0.10 | 0.10 | 380×5 | 380×5 | |
| 11 | 0.15 | 0.10 | 0.25 | 0.20 | - | - | - | 380×5 | 380×5 | |
| 12 | 0.15 | 0.10 | 0.25 | - | 0.20 | - | - | 380×5 | 380×5 | |
| 13 | 0.10 | 0.10 | 0.25 | 0.20 | 0.20 | 0.10 | 0.10 | 380×5 | 380×5 | |
| Comparative sample | 14 | 0.004 | 0.10 | 0.25 | - | - | - | - | 380×5 | 380×5 |
| 15 | 1.05 | 0.10 | 0.25 | - | - | - | - | 380×5 | 380×5 | |
| 16 | 0.15 | 0.004 | 0.25 | - | - | - | - | 380×5 | 380×5 | |
| 17 | 0.15 | 0.46 | 0.25 | - | - | - | - | 380×5 | 380×5 | |
| 18 | 0.15 | 0.10 | 0.04 | - | - | - | - | 380×5 | 380×5 | |
| 19 | 0.15 | 0.10 | 1.1 | - | - | - | - | 380×5 | 380×5 | |
| 20 | 0.10 | 0.10 | 0.25 | 0.20 | 0.20 | 0.10 | 0.10 | 450×5 | 380×5 | |
| 21 | 0.10 | 0.10 | 0.25 | 0.20 | 0.20 | 0.10 | 0.10 | 380×30 | 380×5 | |
| 22 | 0.10 | 0.10 | 0.25 | 0.20 | 0.20 | 0.10 | 0.10 | 250×5 | 380×5 | |
| 23 | 0.10 | 0.10 | 0.25 | 0.20 | 0.20 | 0.10 | 0.10 | 380×5 | 450×5 | |
| 24 | 0.10 | 0.10 | 0.25 | 0.20 | 0.20 | 0.10 | 0.10 | 380×5 | 380×30 | |
| 25 | 0.10 | 0.10 | 0.25 | 0.20 | 0.20 | 0.10 | 0.10 | 380×5 | 250×5 | |
Table 2
| Situation | Alloy number | Copper alloy sheet material microstructure | Alcu alloy film wood property matter | ||||||
| Particle dia surpasses the volume fraction (%) of the dispersoid of 200nm | The average particle diameter of Mg-P dispersoid (nm) | The average particle diameter of Fe-P dispersoid (nm) | Yielding stress (MPa) | Hardness (Hv) | Electric conductivity (%IACS) | Bendability | The stress relaxation rate | ||
| The invention sample | 1 | 2.1 | 30 | 10 | 410 | 136 | 71.0 | Well | 16 |
| 2 | 1.3 | 38 | 6 | 403 | 135 | 68.7 | Well | 16 | |
| 3 | 4.3 | 27 | 25 | 415 | 137 | 65.5 | Well | 19 | |
| 4 | 1.9 | 30 | 15 | 408 | 136 | 68.0 | Well | 15 | |
| 5 | 2.5 | 35 | 23 | 417 | 137 | 63.8 | Well | 19 | |
| 6 | 1.5 | 18 | 10 | 405 | 135 | 69.0 | Well | 17 | |
| 7 | 3.9 | 42 | 12 | 428 | 140 | 63.5 | Well | 15 | |
| 8 | 2.1 | 31 | 10 | 433 | 141 | 62.1 | Well | 16 | |
| 9 | 1.8 | 26 | 8 | 440 | 143 | 61.0 | Well | 14 | |
| 10 | 2.0 | 28 | 9 | 432 | 141 | 63.0 | Well | 15 | |
| 11 | 2.3 | 30 | 11 | 425 | 139 | 67.5 | Well | 15 | |
| 12 | 2.0 | 29 | 10 | 427 | 140 | 67.7 | Well | 16 | |
| 13 | 1.9 | 27 | 9 | 431 | 141 | 63.4 | Well | 15 | |
| Comparative sample | 14 | 1.1 | 40 | 5 | 360 | 126 | 65.0 | Well | 17 |
| 15 | 5.2 | 30 | 28 | 418 | 137 | 64.3 | Failure | 23 | |
| 16 | 1.7 | 29 | 15 | 395 | 133 | 67.5 | Well | 22 | |
| 17 | 3.0 | 58 | 25 | 406 | 136 | 59.0 | Failure | 23 | |
| 18 | 1.3 | 18 | 12 | 400 | 134 | 68.4 | Generally | 22 | |
| 19 | 5.5 | 61 | 14 | 430 | 140 | 61.8 | Failure | 21 | |
| 20 | 5.3 | 55 | 24 | 392 | 133 | 63.5 | Failure | 24 | |
| 21 | 5.2 | 54 | 23 | 390 | 132 | 63.3 | Failure | 24 | |
| 22 | 2.0 | 26 | 8 | 421 | 138 | 57.8 | Generally | 22 | |
| 23 | 5.4 | 55 | 25 | 390 | 132 | 63.8 | Failure | 25 | |
| 24 | 5.2 | 55 | 25 | 387 | 131 | 63.5 | Failure | 25 | |
| 25 | 1.9 | 26 | 8 | 420 | 138 | 58.0 | Generally | 22 | |
Table 3 shows another experimental example, and wherein the amount of the element of the selected property of copper alloy adding and/or other element (impurity) surpasses the preferred upper limit.These samples are the thick thin copper alloy sheet materials of 0.2mm that prepare down in the condition identical with top experimental example (condition that the invention sample is used).By the program of top experimental example, determine the performance of these thin copper alloy sheet materials, for example hardness, electric conductivity and bendability.The results are shown in the table 4.
Invention sample 26 in the table 3 is consistent corresponding to the invention sample 1 of the top experimental example in the table 1 and 2, wherein also stipulates the content of other element (impurity element).
Invention sample 27 contains the A group element in the high total content table 3, i.e. Mn, Ca, Zr, Ag, Cr, Cd, Be, Ti, Co, Ni, Au and Pt.
Invention sample 28 contains the B group element that surpasses in the table 3 of the high total content of 0.1 quality %, i.e. Hf, Th, Li, Na, K, Sr, Pd, N, S, Si, C, Nb, Al, V, Y, Mo, Pb, In, Ga, Ge, As, Sb, Bi, Te, B and norium.
Invention sample 29 and 30 has high Zn content separately.Invention sample 31 and 32 has high Sn content separately.
Principal element Fe, P that these invention samples 27 to 32 have and Mg content and prepare under optimum condition in specialized range of the present invention.The dispersoid requirement of the present invention of these copper alloy satisfies, and have high yielding stress, high rigidity, excellent bendability and excellent stress relaxation performance.But because the high-content of other element, they have than the low electric conductivity of invention sample 26 (corresponding to the invention sample 1 in table 1 and 2).
Comparative sample 33 and 34 has Zn and the Sn content higher than preferred upper limit.Principal element Fe, P that these copper alloys have and Mg content are in specialized range of the present invention, and under optimum condition, prepare, satisfy the requirement of dispersoid of the present invention, and have high yielding stress, high rigidity, excellent bendability and excellent stress relaxation performance.But because high Zn and Sn content, they have than invention sample 27 to 32 remarkable low electric conductivitys.
Table 3
| Situation | Alloy number | The chemical composition of copper alloy sheet material (surplus: Cu and impurity) | Annealing first (℃ * hr) | Second annealing (℃ * hr) | ||||||||
| Fe | P | Mg | Ni | Co | Zn | Sn | The total content of A group | The total content of B group | ||||
| The invention sample | 26 | 0.15 | 0.10 | 0.25 | - | - | - | - | 0.05 | 0.02 | 380×5 | 380×5 |
| 27 | 0.15 | 0.10 | 0.25 | - | - | - | - | 0.55 | 0.02 | 380×5 | 380×5 | |
| 28 | 0.15 | 0.10 | 0.25 | - | - | - | - | 0.12 | 0.12 | 380×5 | 380×5 | |
| 29 | 0.15 | 0.10 | 0.25 | - | - | 1.6 | - | 0.12 | 0.02 | 380×5 | 380×5 | |
| 30 | 0.15 | 0.10 | 0.25 | - | - | 2.5 | - | 0.12 | 0.02 | 380×5 | 380×5 | |
| 31 | 0.15 | 0.10 | 0.25 | - | - | - | 1.5 | 0.12 | 0.02 | 380×5 | 380×5 | |
| 32 | 0.15 | 0.10 | 0.25 | - | - | - | 4.0 | 0.12 | 0.02 | 380×5 | 380×5 | |
| Comparative sample | 33 | 0.15 | 0.10 | 0.25 | - | - | 3.5 | - | 0.12 | 0.02 | 380×5 | 380×5 |
| 34 | 0.15 | 0.10 | 0.25 | - | - | - | 5.5 | 0.12 | 0.02 | 380×5 | 380×5 | |
A group: Mn, Ca, Zr, Ag, Cr, Cd, Be, Ti, Co, Ni, Au and Pt
B group: Hf, Th, Li, Na, K, Sr, Pd, W, S, Si, C, Nb, Al, V, Y, Mo, Pb, In, Ga, Ge, As, Sb, Bi, Te, B and norium.
Table 4
| Situation | Alloy number | Copper alloy sheet material microstructure | Alcu alloy film wood property matter | ||||||
| Particle dia surpasses the volume fraction (%) of the dispersoid of 200nm | The average particle diameter of Mg-P dispersoid (nm) | The average particle diameter of Fe-P dispersoid (nm) | Yielding stress (MPa) | Hardness (Hv) | Electric conductivity (%IACS) | Bendability | Stress relaxation | ||
| The invention sample | 26 | 2.1 | 30 | 10 | 410 | 136 | 71.0 | Well | 16 |
| 27 | 3.0 | 33 | 12 | 415 | 137 | 61.5 | Well | 19 | |
| 28 | 2.5 | 32 | 11 | 412 | 136 | 63.3 | Well | 18 | |
| 29 | 2.1 | 30 | 11 | 445 | 144 | 60.4 | Well | 16 | |
| 30 | 2.1 | 31 | 10 | 454 | 146 | 58.8 | Well | 15 | |
| 31 | 1.8 | 25 | 8 | 450 | 145 | 59.3 | Well | 14 | |
| 32 | 1.7 | 24 | 7 | 472 | 150 | 56.2 | Well | 13 | |
| Comparative sample | 33 | 2.1 | 31 | 10 | 459 | 147 | 54.7 | Well | 15 |
| 34 | 1.7 | 24 | 7 | 479 | 152 | 52.4 | Well | 13 | |
As above-mentioned,, the Cu-Fe-P alloy with excellent bendability and excellent stress relaxation performance can be provided, and not lose high strength and high conductivity according to the present invention.Therefore, can be except the IC lead frame that is used for semiconducter device with the copper alloy that obtains, also be used for lead frame, junctor, terminating unit, switching element, rly. and other purposes, play a part miniaturization and weight electronics and electric elements, need high strength, high conductivity, can guarantee in the purposes of the excellent bendability of quirk and excellent stress relaxation performance at these.
Though disclose the present invention according to embodiment preferred,, should be noted in the discussion above that the present invention can specialize in every way under the condition that does not depart from the principle of the invention to help its better understanding.Therefore, should be understood that, present invention resides in do not depart from the present invention under the condition of the described principle of appended claim all possible embodiment and to shown in the change of embodiment.
Claims (7)
1. an Albatra metal-, it has bendability and stress relaxation performance, and comprise the P of Fe, 0.01 to 0.4 quality % of 0.01 to 1.0 quality % and the Mg of 0.1 to 1.0 quality %, wherein surplus is copper and unavoidable impurities, wherein to surpass the volume fraction of the dispersoid of 200nm be 5% or lower to the particle dia separately of copper alloy, and wherein separately particle dia be that 200nm or average particle diameter lower and that contain the dispersoid of Mg and P are 5nm or higher and 50nm or lower.
2. according to the copper alloy of claim 1, wherein particle dia is that 200nm or average particle diameter lower and that comprise the dispersoid of Fe and P are 1nm or higher and 20nm or lower separately.
3. according to the copper alloy of one of claim 1 and 2, also comprise the Ni of 0.01 to 1.0 quality % and at least one among the Co.
4. according to any one copper alloy of claim 1 to 3, also comprise the Zn of 0.005 to 3.0 quality %.
5. according to any one copper alloy of claim 1 to 4, also comprise the Sn of 0.01 to 5.0 quality %.
6. according to any one copper alloy of claim 1 to 5, wherein the total content of the Mn of copper alloy, Ca, Zr, Ag, Cr, Cd, Be, Ti, Co, Ni, Au and Pt is 1.0 quality % or lower.
7. according to any one copper alloy of claim 1 to 6, wherein the total content of the Hf of copper alloy, Th, Li, Na, K, Sr, Pd, W, S, Si, C, Nb, Al, V, Y, Mo, Pb, In, Ga, Ge, As, Sb, Bi, Te, B and norium is 0.1 quality % or lower.
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