CN1926253A - Copper alloy - Google Patents
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- CN1926253A CN1926253A CN 200580006329 CN200580006329A CN1926253A CN 1926253 A CN1926253 A CN 1926253A CN 200580006329 CN200580006329 CN 200580006329 CN 200580006329 A CN200580006329 A CN 200580006329A CN 1926253 A CN1926253 A CN 1926253A
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Abstract
A copper alloy, which contains: a precipitate X composed of Ni and Si; and a precipitate Y that comprises Ni or Si or neither Ni nor Si, wherein the precipitate X has a grain size of 0.001 to 0.1mum, and the precipitate Y has a grain size of 0.01 to 1mum.
Description
Technical field
The present invention relates to a kind of copper alloy that on performance, improves and improving.
Background technology
Up to now, usually except that iron, copper-based material that electroconductibility and thermal conductivity are fabulous such as phosphor bronze, red brass (red brass) and brass have been widely used as the material of Electrical and Electronic apparatus and element (Electrical and Electronic instrument).
Recently, the demand of the miniaturization of Electrical and Electronic apparatus and element, lightness and associated high density packing (packaging) is increased, and its copper-based material that adopts also needs different characteristics.The example of desired fundamental characteristics comprises mechanical property, electroconductibility, proof stress slackness (stressrelaxation resistance) and bending property.Wherein, strong request improves tensile strength and bending property, to satisfy recent demand to the said products parts or part miniaturization.
These demands depend on the shape of parts etc., and concrete requirement comprises: the tensile strength that 720MPa or 720MPa are above and the bending property (wherein R represents bending radius, and t represents thickness) of R/t≤1; The tensile strength that 800MPa or 800MPa are above and the bending property of R/t＜1.5; Or the tensile strength more than 900MPa or the 900MPa and the bending property of R/t＜2.Desired characteristic has reached alloy such as phosphor bronze, red brass and the unappeasable level of brass of the commercially available scale operation of routine.By following method these alloys intensity is separately improved: being included in the copper as sosoloid, and resulting alloy with sosoloid to be carried out cold working such as rolling or stretching with the copper of matrix phase significantly different tin or zinc on atomic radius.This method can provide high-strength material by using big cold working ratio (cold working ratio), but is to use big cold working ratio (more than common 50% or 50%) to be it has been generally acknowledged that the bending property that can reduce resulting alloy material significantly.This method generally includes the combination of solution strengthening and work strengthening.
The enhancement method that replaces is the precipitation strength method, and it is included in and forms nano level precipitate in the material.The precipitation strength method has the advantage that improves intensity simultaneously and improve specific conductivity, and is used for many alloys.
Wherein, by nickel and silicon are added in the copper, form the precipitate of forming by nickel and silicon, the reinforced alloys of preparation, be so-called Corson alloy (Corson alloy), compare with many other sedimentation type alloys (precipitation hardening alloy) and have significantly high reinforcement performance.This enhancement method also is used for some commercially available alloys (for example CDA70250, the registration alloy of Copper Development Association (CDA)).When common alloy through precipitation strength is used as terminal/connector material (terminal/connectormaterial), produce this alloy by comprising following two important heat treated production technique.First thermal treatment is included near high temperature (usually at 700 ℃ or the higher) thermal treatment down the fusing point, and promptly so-called solution treatment makes by casting or the sedimentary nickel of hot rolling and silicon to be included in the copper matrix as sosoloid.Thermal treatment for the second time is included in than thermal treatment under the low temperature of solution treatment, and promptly so-called ageing treatment (agingtreatment) is separated out the nickel and the silicon that are solid solution condition under the high temperature as precipitate.This enhancement method has utilized high temperature and low temperature to add the concentration difference as the nickel and the silicon of sosoloid in the copper down, and this method this in producing the sedimentation type alloy, be well-known technology.
The Corson alloy example that is applicable to Electrical and Electronic apparatus and element comprises have the regulation crystal particle diameter alloy of (crystal grain size).
Yet the sedimentation type alloy has following point: crystal particle diameter increase to produce coarse grain during solution treatment, and the crystal particle diameter during solution treatment remains unchanged and become the crystal particle diameter of product, because ageing treatment does not comprise recrystallize usually.The add-on that increases nickel or silicon then requires solution treatment under higher temperature, and this causes making crystal particle diameter trend towards increasing by the thermal treatment in the short period of time and produces coarse grain.The coarse grain of Chu Xianing can produce the significantly reduced problem of bending property by this way.
Replacedly, the method that improves the copper alloy bending property comprises that adding manganese, nickel and phosphorus separates out compound with cross reaction, and does not use nickel-silicon precipitate.
Yet this alloy has at the most the approximately tensile strength of 640MPa, and this is not enough to satisfy recent high strength demand to the parts miniaturization.Silicon is joined the amount that has reduced nickel-phosphorus precipitate in the copper alloy, thereby reduce physical strength and specific conductivity.In addition, excess silicon and phosphorus cause that the crack goes wrong during hot-work.
Copper alloy is required to have the tensile strength of height, and bending property and specific conductivity are difficult to keep bending property yet improved tensile strength.
Other and feature and advantage further of the present invention will embody from following explanation more fully.
Summary of the invention
According to the present invention, provide following:
(1) one Albatra metal-comprises:
The precipitate X that forms by nickel and silicon; With
Comprise nickel or silicon or comprise that neither nickel does not comprise the precipitate Y of silicon yet,
Wherein precipitate X has the particle diameter of 0.001 to 0.1 μ m, and precipitate Y has the particle diameter of 0.01 to 1 μ m.
(2) according to the copper alloy of above-mentioned (1), wherein precipitate Y has the fusing point that is higher than solid solution temperature.
(3) according to the copper alloy of above-mentioned (1) or (2), it comprises the nickel of 2 to 5 quality %, 0.3 to the silicon of 1.5 quality % and the boron of 0.005 to 0.1 quality %, surplus is copper and unavoidable impurities, during wherein the numbers of particles of precipitate X is every square millimeter in every square millimeter 20 to 2000 times of the numbers of particles of precipitate Y.
(4) according to the copper alloy of above-mentioned (1) or (2), it comprises the nickel of 2 to 5 quality %, the silicon of 0.3 to 1.5 quality %, the manganese of 0.01 to 0.5 quality %, phosphorus with 0.01 to 0.5 quality %, surplus is copper and unavoidable impurities, during wherein the numbers of particles of precipitate X is every square millimeter in every square millimeter 20 to 2000 times of the numbers of particles of precipitate Y.
(5) according to the copper alloy of above-mentioned (1) or (2), it comprises the nickel of 2 to 5 quality %, the silicon of 0.3 to 1.5 quality %, the boron of 0.005 to 0.1 quality %, the manganese of 0.01 to 0.5 quality % and the phosphorus of 0.01 to 0.5 quality %, surplus is copper and unavoidable impurities, during wherein the numbers of particles of precipitate X is every square millimeter in every square millimeter 20 to 2,000 times of the numbers of particles of precipitate Y.
(6) according to the copper alloy of above-mentioned (1) or (2), wherein the numbers of particles of precipitate X is 10 in every square millimeter
8To 10
12Individual, the numbers of particles of precipitate Y is 10 in every square millimeter
4To 10
8Individual.
(7) according to any one copper alloy in above-mentioned (1) to (6), it comprises at least a element in aluminium, arsenic, hafnium, zirconium, chromium, titanium, carbon, iron, phosphorus, indium, calcium halophosphate activated by antimony andmanganese, tantalum and the vanadium of being selected from of 0.005 to 0.5 quality %.
(8) according to the copper alloy of above-mentioned (6) or (7), wherein precipitate Y is by at least a composition the in aluminium-arsenic, aluminium-hafnium, aluminum-zirconium, aluminium-chromium, titanium-carbon, copper-titanium, copper-zirconium, chromium-silicon, iron-phosphorus, iron-silicon, iron-zirconium, indium-nickel, magnesium-calcium halophosphate activated by antimony andmanganese-silicon, nickel-antimony, silicon-tantalum and the vanadium-zirconium.
(9) according to any one the copper alloy in above-mentioned (3) to (8), it also comprises at least a element in the magnesium of the zinc of the tin that is selected from 0.1 to 1.0 quality %, 0.1 to 1.0 quality % and 0.05 to 0.5 quality %.
(10) according to any one the copper alloy in above-mentioned (1) to (9), be used for electric or electronic equipments and element.
Embodiment
Below explain in detail the present invention.
The present inventor furthers investigate the copper alloy that is applicable to electric component and electronic unit, we have found that the particle diameter of nickel in the copper alloy structure-silicon precipitate and other precipitate, its distribution density than and to the relation between the inhibition of too big grain growing.As a result, the present inventor has realized the present invention, promptly has the copper alloy of fabulous tensile strength and good bending property.
To describe the preferred embodiment of copper alloy of the present invention below in detail.
The present invention relates to the control of alloy crystal particle diameter.Specifically, the present inventor experimentizes to the method from two aspects control particle diameter, we obtained the special alloy structure of the present invention with and preferred group become.
At first, the present inventor has searched the element that crystal particle diameter is increased.Even the present inventor finds under the high temperature of solution treatment, the precipitate of being made up of nickel and boron can not form any sosoloid yet in the copper matrix phase, and this precipitate is present in copper matrix phase and the precipitate particulate crystal grain, has the effect and the effect that suppress the matrix grain growth.Proof aluminium-arsenic, aluminium-hafnium, aluminum-zirconium, aluminium-chromium, titanium-carbon, copper-titanium, copper-zirconium, chromium-silicon, iron-phosphorus, iron-silicon, iron-zirconium, indium-nickel, magnesium-calcium halophosphate activated by antimony andmanganese-silicon, nickel-antimony, silicon-tantalum and vanadium-zirconium have also confirmed this effect and effect.
Secondly, the present inventor has searched the element that is used as initial recrystallization nucleus during solution treatment.The present inventor has found a kind of intermetallic compound (intermetallic compound), the precipitate that it is made up of manganese and phosphorus, nucleation site during as recrystallize under solid solution temperature, and find can form more polycrystalline grain (nucleation) than the situation that does not add the precipitate of forming by manganese and phosphorus.More the formation of polycrystalline grain causes interfering with each other of crystal grain during grain growth, thereby suppresses grain growth.This effect and the effect of nucleation site when aluminium-arsenic, aluminium-hafnium, aluminum-zirconium, aluminium-chromium, titanium-carbon, copper-titanium, copper-zirconium, chromium-silicon, iron-phosphorus, iron-silicon, iron-zirconium, indium-nickel, magnesium-calcium halophosphate activated by antimony andmanganese-silicon, nickel-antimony, silicon-tantalum and vanadium-zirconium have also confirmed recrystallize.
And the significant effect that manganese-phosphorus and nickel-boron are separated out simultaneously also is confirmed, and this effect is not that the institute that adds up of the effect when only manganese-phosphorus or nickel-boron being used separately is getable.
Even importantly can in the copper matrix, not form any sosoloid at above-mentioned precipitate during the solution treatment yet.That is, precipitate must have the fusing point that is higher than solid solution temperature.As long as fusing point is higher than solid solution temperature, this precipitate is not limited to above-mentioned precipitate.And the present invention also comprises any precipitate except above-mentioned precipitate.In the present invention, the fusing point precipitate that is higher than solid solution temperature has played the effect that prevents the coarse grain growth or form many crystal grain (nucleation) during by recrystallize as nucleation site during solution treatment.
Copper alloy of the present invention is a kind of low-cost high performance copper alloy, have fabulous bending property and other superperformance, be particularly useful for various Electrical and Electronic machine tool and the elements that have electronic component, for example launch vehicle terminal/junctor, rly. and switch.
Next, will the effect of each alloying element and the preferable range of effect and alloy adding be described.
Nickel and silicon can form the nickel-silicon precipitate of precipitation strength by the additional proportion of control nickel and silicon, thereby improve the physical strength of copper alloy.The add-on of nickel is 2 to 5 quality % normally, preferred 2.1 to 4.6 quality %.The nickel amount is 3.5 to 4.6 quality % more preferably, satisfying the bending property of 800MPa or the tensile strength more than the 800MPa and R/t＜1.5, or the above tensile strength of 900MPa or 900MPa and the bending property of R/t＜2.Nickel amount very little provides few separating out and hardening capacity, causes the physical strength deficiency, and too many nickel amount then causes significantly low specific conductivity.
In addition, known silicon provides maximum strengthening effect when adding about nickel amount 1/4 (in quality %), and this amount is preferred.Too many silicon add-on is easy to cause that ingot bar (ingot) breaks during hot-work, therefore considers this point, has stipulated the upper limit of silicon add-on.The silicon add-on is 0.3 to 1.5 quality % normally, preferred 0.5 to 1.1 quality %, more preferably 0.8 to 1.1 quality %.
The nickel of boron and adding forms precipitate.The effect of boron is that boron is to suppress the crystal particle diameter increase to become the too element of big (huge) during solution treatment as mentioned above, but boron does not participate in precipitation strength.From experiment, the inventor has confirmed the boron of common needs 0.005 to 0.1 quality %, and the boron of preferred 0.01 to 0.07 quality % is just had that effect.Boron add-on too many during casting causes too big crystallized product, causes the ingot bar quality problems, and boron add-on does not very little then add effect.
The precipitate of manganese and phosphorus has played the effect that forms the crystal grain nucleation site during solution treatment, but this precipitate does not participate in precipitation strength.The content that adds manganese and phosphorus all is that 0.01 quality % or 0.01 quality % are above to 0.5 quality % or below the 0.5 quality %, the material of preferred 0.02 to 0.3 quality % has confirmed this effect usually.The very few material of manganese and phosphorus amount separately is without any effect.In addition, when manganese and phosphorus add-on separately were too many, it caused the generation crack problem during hot-work, hindered and was processed into thin plate or thin slice.
It is too big to provide the increase of inhibition crystal particle diameter to become in solution treatment, or other example of the precipitate of the effect of the nucleation site of formation crystal grain comprises aluminium-arsenic, aluminium-hafnium, aluminum-zirconium, aluminium-chromium, titanium-carbon, copper-titanium, copper-zirconium, chromium-silicon, iron-phosphorus, iron-silicon, iron-zirconium, indium-nickel, magnesium-calcium halophosphate activated by antimony andmanganese-silicon, nickel-antimony, silicon-tantalum and vanadium-zirconium.Copper alloy preferably contains at least a element that is selected from aluminium, zirconium, chromium, carbon, titanium, iron, indium, arsenic, hafnium, antimony, tantalum and the vanadium, and its amount is generally 0.005 to 0.5 quality % separately, and preferred 0.01 to 0.4 quality % is to show above-mentioned effect.If the add-on of these elements is too big, resulting alloy forms too big crystallized product during casting, and causes resulting ingot bar quality problems, and if add-on is too little, do not have additive effect (addition effect).
In addition, preferably add zinc, tin and magnesium and further improve performance.
The preferred zinc that adds 0.1 to 1.0 quality %.Zinc is the element that forms sosoloid in matrix, but the adding of zinc improves solder embrittlement (solder embrittlement) significantly.The preferred main application of alloy of the present invention is Electrical and Electronic apparatus and element and electronic unit material such as launch vehicle terminal/junctor, rly. and switch.Great majority in them are to connect by soft soldering, and therefore improving solder embrittlement is an important basic fundamental.
In addition, the adding of zinc can reduce the fusing point of alloy, precipitate that control is made up of nickel and boron and the precipitate formed by manganese and phosphorus form state.Two kinds of precipitates all during curing form.Therefore, the high solidification value of alloy increases particle diameter, and the effect of effect that the crystal particle diameter that suppresses precipitate is increased and forms the crystal grain nucleation site is little.The undergage of zinc add-on is decided to be 0.1 quality %, because it is the minimum quantity that improves solder embrittlement.The upper limit of zinc add-on is defined as 1.0 quality %, can reduce specific conductivity because surpass the zinc add-on of 1.0 quality %.
With regard to its purposes, tin and magnesium also are preferred elements.The adding of tin and magnesium has the effect that improves creep resistance, and this is to emphasize in electronic equipments and element terminal/junctor.This effect is also referred to as the loose property of proof stress, and it is the important basic fundamental of inferring terminal/junctor reliability.Add tin or magnesium separately and can improve creep resistance, but tin and magnesium can further improve creep resistance by Overlay.
The undergage of tin add-on is decided to be 0.1 quality %, because it is the minimum quantity that improves creep resistance.The upper limit of tin add-on is defined as 1 quality %, can reduce specific conductivity because surpass the tin add-on of 1 quality %.
The undergage of magnesium add-on is decided to be 0.05 quality %, because magnesium add-on does not very little improve the effect of creep resistance.The upper limit of magnesium add-on is defined as 0.5 quality %, not only makes effect saturated but also can reduce hot workability again because surpass the magnesium add-on of 0.5 quality %.
Tin and magnesium have the effect of quickening to form the precipitate of being made up of nickel and silicon.The tin and the magnesium that importantly add preferred amounts are as the small epipole of precipitate.
Secondly, will the alloy structure of copper alloy of the present invention be described.
Precipitate X is a kind of intermetallic compound of being made up of nickel and silicon, and its particle diameter is 0.001 to 0.1 μ m, is preferably 0.003 to 0.05 μ m, more preferably 0.005 to 0.02 μ m.Too little particle diameter can not improve intensity; And particle diameter promptly is common so-called overaging state greatly, cause physical strength to can not get improving and bending property poor.
(in this manual, comprise claims) here, the precipitate (one or more) except the precipitate of the intermetallic compound be made up of nickel and silicon is called precipitate Y.Precipitate Y has by interacting the effect of crystal grain thinning with nickel-silicon precipitate X.Under the situation that has precipitate X to exist, this effect is significant.The particle diameter of precipitate Y is preferably 0.01 to 1 μ m, and more preferably 0.05 to 0.5 μ m most preferably is 0.05 to 0.13 μ m.Too little particle diameter does not act on suppressing grain growth and increasing the nucleation site number, and too big particle diameter then reduces bending property.
Then, will the number of precipitate X and Y be described.The numbers of particles of precipitate X is 20 to 2,000 times of numbers of particles of precipitate Y preferably.This is outstanding especially because of bending property in above-mentioned scope.When the numbers of particles of precipitate X very little the time, it does not reach the physical strength index, and when its number was too many, it can reduce bending property.The numbers of particles of precipitate X is more preferably 100 to 1500 times of numbers of particles of precipitate Y.Here, the numbers of particles of the precipitate meaning is the mean value of unit volume.
When precipitate Y is an intermetallic compound, it is a kind of intermetallic compound except nickel-silicon, and be selected from aluminium-arsenic, aluminium-hafnium, aluminum-zirconium, aluminium-chromium, titanium-carbon, copper-titanium, copper-zirconium, chromium-silicon, iron-phosphorus, iron-silicon, iron-zirconium, indium-nickel, magnesium-calcium halophosphate activated by antimony andmanganese-silicon, nickel-antimony, silicon-tantalum and vanadium-zirconium, preferably every square millimeter 10 of the numbers of particles of precipitate X
8To 10
12Individual, and preferably every square millimeter 10 of the numbers of particles of precipitate Y
4To 10
8Individual.This is because above-mentioned scope can provide outstanding especially bending property.If the precipitate number very little, resulting alloy may not reach the physical strength index.On the other hand, if the precipitate number is too many, the bending property of resulting alloy may be poor.The numbers of particles of precipitate X is more preferably every square millimeter 5 * 10
9To 6 * 10
11Individual, and more preferably every square millimeter 10 of the numbers of particles of precipitate Y
4To 4 * 10
7Individual.
Along with the amount increase of nickel and silicon, the more remarkable effect of X and Y.Gui Ding above-mentioned concrete X and Y cause and have obtained the above tensile strength of 800MPa or 800MPa and the bending property of R/t＜1.5 first in the present invention, or the tensile strength more than 900MPa or the 900MPa and the bending property of R/t＜2, this is the performance that does not reach so far.
The precipitate of mentioning in the present invention comprises for example intermetallic compound, carbide, oxide compound, sulfide, nitride, mixture (compound) (sosoloid) and metal element (elementary metals).
The crystal particle diameter of copper alloy of the present invention is generally 20 μ m or below the 20 μ m, preferred 10.0 μ m or below the 10.0 μ m.Too big crystal particle diameter can not provide the above tensile strength of 720MPa or 720MPa and the bending property of R/t＜2.The crystal particle diameter of copper alloy of the present invention is 8.5 μ m or below the 8.5 μ m more preferably.Lower limit to crystal particle diameter has no particular limits, but the crystal particle diameter of copper alloy is generally 0.5 μ m or more than the 0.5 μ m.
The example of the production method of copper alloy of the present invention comprises: fusing has the copper alloy of above-mentioned preferred elements composition; Be cast into ingot bar; With come this ingot bar of hot rolling by this ingot bar being heated with 20-200 ℃/hour heat-up rate, 850-1050 ℃ of following hot rolling ingot bar 0.5-5 hour, after hot rolling, this ingot bar is quenched into 300-700 ℃ finishing temperature then.Form precipitate X and Y with such method.For example, after hot rolling,, be given thickness with resulting Alloy Forming by solution treatment, annealing and cold rolling combination.
Solution treatment is a kind ofly nickel and silicon are separated out and to form sosoloid and the thermal treatment of recrystallize simultaneously once more.Can regulate the temperature of solution treatment according to the nickel add-on.For example, be 2.0 quality % or more than the 2.0 quality % but less than 2.5 quality % for the nickel amount, preferably 650 ℃ of solid solution temperatures; For the nickel amount is 2.5 quality % or 2.5 above but less than 3.0 quality %, preferably 800 ℃ of solid solution temperatures; For the nickel amount is 3.0 quality % or more than the 3.0 quality % but less than 3.5 quality %, preferably 850 ℃ of solid solution temperatures; For the nickel amount is 3.5 quality % or more than the 3.5 quality % but less than 4.0 quality %, preferably 900 ℃ of solid solution temperatures; For the nickel amount is 4.0 quality % or more than the 4.0 quality % but less than 4.5 quality %, preferably 950 ℃ of solid solution temperatures; And for the nickel amount from 4.5 quality % to 5.0 quality %, preferably 980 ℃ of solid solution temperatures.
For example, the material that contains 3.0 quality % nickel allows the nickel and the silicon of fully having separated out form sosoloid again 850 ℃ thermal treatment, and obtains 10 μ m or the following crystal grain of 10 μ m.Yet, cause that less than the thermal treatment under the uniform temp of the alloy of 3.0 quality % grain growing becomes particle diameter separately to be not less than the big particle of 10 μ m at nickel content.And too big nickel amount can not form ideal solution state, and can not improve physical strength by ageing treatment afterwards.
The present invention is to bending property, provides obvious improvement in tensile strength for the bending property of 800MPa or the high strength copper alloy more than the 800MPa especially.And the present invention improves on the bending property of anti-stretch-draw intensity less than the copper alloy of 800MPa equally.
Copper alloy bending property of the present invention is good, and has the high intensity of drawing, and preferably is applicable to lead frame, junctor and the terminal material of Electrical and Electronic apparatus and element, is particularly useful for junctor or line end material, rly. and the switch of automobile.
According to the present invention, can provide bending property the conventional alloy good copper alloy more identical than tensile strength, it is particularly preferred for Electrical and Electronic apparatus and element, be by grain size that adds control copper-nickel-silicon alloys such as boron, manganese, phosphorus, aluminium, zirconium, chromium, carbon, titanium, iron, indium, arsenic, hafnium, antimony, tantalum, vanadium and the alloy that except above-mentioned alloying element, also contains tin, zinc and magnesium, satisfied simultaneously very high tensile strength and the fabulous bending property (R/t) of obtaining.
Embodiment
To describe the present invention in more detail based on following embodiment, but the present invention is not limited to these embodiment.
(embodiment 1)
Melt alloy in the high-frequency melting stove, it is copper and unavoidable impurities that this alloy contains the nickel of 4.2 quality %, the silicon of 1.0 quality % and chromium, the surplus of following amount.The chromium amount that joins in the copper alloy is respectively: embodiment 1 is 0.05 quality %, embodiment 2 is 0.15 quality %, embodiment 3 is 0.25 quality %, embodiment 4 is 0.5 quality %, embodiment 5 is 0.7 quality %, and embodiment 6 is 0.9 quality %, and comparative example 1 is 0.005 quality %, comparative example 2 is 0.2 quality %, and comparative example 3 is that 0.5 quality % and comparative example 4 are 0.8 quality %.With 10-30 ℃/second the speed of cooling resulting alloy of casting, be that 30 millimeters, width are that 100 millimeters and length are 150 millimeters ingot bar thereby obtain thickness.This crystal block was kept 1 hour down at 900 ℃, pass through hot rolling then, the production thickness t is 12 millimeters a hot-rolled sheet.In both sides this plate is carried out 1 millimeter thickness to 10 millimeter thickness t of bevel (chamfering), then by cold rolling thickness t=0.167 millimeter of being processed into.This sheet material was 950 ℃ of following solution treatment 20 seconds.
This sheet material passes through shrend immediately after solution treatment.Then, this alloy is separately through ageing treatment 450 to 500 ℃ under 2 hours, and is more cold rolling than (working ratio) with 10% processing then, thus the sample of acquisition t=0.15 millimeter.
Following properties according to following method test of mentioning and the thus obtained sample of mensuration.
A. specific conductivity
In the thermostatic bath that maintains 20 ℃ (± 0.5 ℃),, thereby calculate specific conductivity by the resistivity of four-terminal method measure sample.Distance between the terminal is set to 100 millimeters.
B. tensile strength
On the direction parallel,, measure their tensile strength, obtain their mean value according to JIS Z 2241 from sample cutting and according to 3 testpieces of JIS Z 2201-13B preparation with rolling direction.
C. bending property
Will be on the direction parallel with rolling direction cutting out width from sample is that 10 millimeters and length are the test specimen of 25 millimeters sizes.With radius of curvature R is 0,0.1,0.15,0.2,0.25,0.3,0.4,0.5 or 0.6 (millimeter), and its bending axis is made resulting test specimen the W-bending of 90 degree perpendicular to rolling direction.Detect by an unaided eye the crack whether occurs by opticmicroscope, and whether can observe the crack with inspection with the sem observation bending position at curved part with 50 x magnifications.Represent evaluation result (wherein R represents bending radius, and t represents plate thickness) with R/t, (limit) maximum value R calculates R/t when occurring by the use crack.Form the crack during at R=0.1 if do not form the crack when R=0.15, because thickness of sample (t)=0.15 millimeter, so obtain R/t=0.15/0.15=1, this is indicated in the following table.
D. the particle diameter of precipitate and distribution density
It is 3 millimeters discoid that sample is struck out diameter, uses the polishing method (twinjet polishing method) of twinjet to make resulting disk shaped samples through the film polishing then.The transmission electron microscope that with acceleration voltage is 300 kilovolts is taken a picture (5,000 and 100,000 x magnification) to any 3 positions of resulting sample, measures the particle diameter and the density of precipitate then according to photograph.According to following manner the particle diameter and the density of precipitate are measured: the incident beam position angle is navigated to [001], at high power photograph (100,000 x magnification) measure the fine particle number of the precipitate X that is made up of nickel-silicon in when n=100 (n represents the number of field of view), this is because precipitate X is finer; On the other hand, measure at the numbers of particles of precipitate Y during at n=10 in the low power photograph (5,000 x magnification); Thereby eliminate the partial deviations of number.This number is converted into the number (/ square millimeter) of per unit area.
As showing from result shown in the table 1, the copper alloy of each embodiment of the present invention all has fabulous performance aspect physical strength and the bending property two.Yet with above-mentioned opposite, the particle diameter of precipitate X does not fall in the scope of the present invention's regulation in comparative example 1 and 3 copper alloy separately, and the particle diameter of precipitate Y does not fall in the scope of the present invention's regulation in comparative example 2 and 4 copper alloy separately.Therefore, these comparative examples copper alloy separately, even they have identical with embodiment basically physical strength separately, its bending property is also poor significantly, is R/t 〉=2.
Table 1
| The particle diameter μ m of X | The particle diameter μ m of Y | X numbers of particles/Y numbers of particles | Tensile strength MPa | Bending property R/t | |
| Embodiment 1 | 0.003 | 0.03 | 100 | 911 | 1.67 |
| Embodiment 2 | 0.03 | 0.05 | 320 | 921 | 1.67 |
| Embodiment 3 | 0.08 | 0.09 | 210 | 908 | 1.67 |
| Embodiment 4 | 0.02 | 0.08 | 530 | 903 | 1.67 |
| Embodiment 5 | 0.07 | 0.02 | 360 | 921 | 1.67 |
| Embodiment 6 | 0.04 | 0.03 | 830 | 918 | 1.67 |
| Comparative example 1 | 0.0003 | 0.05 | 780 | 912 | 2 |
| Comparative example 2 | 0.04 | 0.003 | 150 | 925 | 2 |
| Comparative example 3 | 0.5 | 0.03 | 950 | 923 | 2.67 |
| Comparative example 4 | 0.06 | 1.2 | 740 | 915 | 3.3 |
(embodiment 2)
With the method the same with embodiment 1, to having composition as shown in table 2 separately, and surplus is that the copper alloy of copper and unavoidable impurities is tested and evaluated.Making method is identical with embodiment 1 with measuring method.
As showing from result shown in the table 2, the copper alloy of each embodiment of the present invention all has fabulous performance aspect physical strength and the bending property two.Yet on the contrary, therefore nickel content can not reach the tensile strength index less than the lower limit of preferable range of the present invention in the copper alloy of comparative example 5.The copper alloy of comparative example 6 has big nickel amount, and occurs the crack during processing, and therefore can not make the material that is used to evaluate.Comparative example 7 and 8 copper alloy separately boron content and the ratio of X number and Y number do not fall within the scope separately of the present invention's regulation, therefore can not reach physical strength index and bending property simultaneously.
Table 2
| Element | The particle diameter μ m of X | The particle diameter μ m of Y | X numbers of particles/Y numbers of particles | Tensile strength MPa | Bending property R/t | Specific conductivity %IACS | ||||
| Ni quality % | Si quality % | B quality % | Other quality % | |||||||
| Embodiment 7 | 2.20 | 0.50 | 0.050 | - | 0.002 | 0.13 | 150 | 721 | 1 | 42.0 |
| Embodiment 8 | 2.70 | 0.64 | 0.060 | - | 0.002 | 0.05 | 350 | 772 | 1 | 41.0 |
| Embodiment 9 | 3.30 | 0.79 | 0.040 | - | 0.002 | 0.5 | 330 | 813 | 1.5 | 39.0 |
| Embodiment 10 | 3.80 | 0.90 | 0.050 | - | 0.003 | 0.18 | 500 | 861 | 1.5 | 37.0 |
| Embodiment 11 | 4.20 | 1.00 | 0.040 | - | 0.002 | 0.7 | 450 | 903 | 1.5 | 35.5 |
| Embodiment 12 | 3.80 | 0.90 | 0.009 | - | 0.002 | 0.3 | 1050 | 844 | 1.5 | 37.0 |
| Embodiment 13 | 3.80 | 0.90 | 0.085 | -- | 0.003 | 0.05 | 320 | 838 | 1.5 | 37.0 |
| Embodiment 14 | 4.20 | 1.00 | 0.008 | - | 0.002 | 0.24 | 1400 | 913 | 1.67 | 35.5 |
| Embodiment 15 | 4.20 | 1.00 | 0.094 | - | 0.002 | 0.8 | 630 | 909 | 1.67 | 35.5 |
| Embodiment 16 | 2.25 | 0.51 | 0.030 | Zn0.15 | 0.002 | 0.11 | 150 | 721 | 1 | 41.0 |
| Embodiment 17 | 3.35 | 0.82 | 0.050 | Sn0.12 Mg0.07 | 0.002 | 0.23 | 340 | 811 | 1.5 | 38.0 |
| Embodiment 18 | 4.05 | 0.98 | 0.065 | Zn0.95 Sn0.80 Mg0.40 | 0.002 | 0.28 | 550 | 902 | 1.67 | 36.2 |
| Comparative example 5 | 1.50 | 0.25 | 0.050 | - | 0.002 | 0.1 | 450 | 600 | 1 | 45.0 |
| Comparative example 6 | 6.50 | 1.50 | 0.060 | - | Do not make sample | |||||
| Comparative example 7 | 3.80 | 0.90 | 0.001 | - | 0.002 | 0.003 | ＞2000 | 866 | 2 | 37.0 |
| Comparative example 8 | 3.80 | 0.90 | 0.500 | - | 0.001 | 1.2 | 10 | 780 | 2.67 | 37.0 |
Annotate: "-" do not add
(embodiment 3)
With the method the same with embodiment 1, to having composition as shown in table 3 separately, and surplus is that the copper alloy of copper and unavoidable impurities is tested and evaluated.Making method is identical with embodiment 1 with measuring method.
As showing from result shown in the table 3, the copper alloy of each embodiment of the present invention all has fabulous performance aspect physical strength and the bending property two.Yet on the contrary, the nickel of the copper alloy of comparative example 9 and silicone content be less than the present invention's lower limit of preferable range separately, therefore inaccessiable tensile strength index.The copper alloy of comparative example 10 has big nickel and silicone content, and occurs the crack during processing, and therefore can not produce the material that is used to evaluate.The copper alloy of comparative example 11 to 14 separately manganese content and/or phosphorus content do not fall into the present invention regulation scope in, and/or the ratio of the numbers of particles of X and the numbers of particles of Y does not fall in the scope of the present invention's regulation.Therefore, the copper alloy of these comparative examples bending property separately is poor, and R/t is more than 2 or 2.
Table 3
| Element | The particle diameter μ m of X | The particle diameter μ m of Y | X numbers of particles/Y numbers of particles | Tensile strength MPa | Bending property R/t | Specific conductivity %IACS | ||||||
| Ni quality % | Si quality % | Mn quality % | P quality % | Other quality % | ||||||||
| Embodiment 19 | 2.20 | 0.50 | 0.100 | 0.100 | - | 0.002 | 0.08 | 450 | 728 | 1 | 42.0 | |
| Embodiment 20 | 2.70 | 0.64 | 0.120 | 0.090 | - | 0.002 | 0.1 | 480 | 758 | 1.5 | 41.0 | |
| Embodiment 21 | 3.30 | 0.79 | 0.080 | 0.110 | - | 0.003 | 0.5 | 1020 | 811 | 1.5 | 39.0 | |
| Embodiment 22 | 3.80 | 0.90 | 0.110 | 0.120 | - | 0.002 | 0.12 | 140 | 883 | 1.5 | 37.0 | |
| Embodiment 23 | 4.20 | 1.00 | 0.090 | 0.100 | - | 0.002 | 0.44 | 90 | 921 | 1.67 | 35.5 | |
| Embodiment 24 | 3.80 | 0.90 | 0.020 | 0.030 | - | 0.002 | 0.13 | 420 | 873 | 1.5 | 37.0 | |
| Embodiment 25 | 3.80 | 0.90 | 0.450 | 0.230 | - | 0.003 | 0.07 | 1080 | 833 | 1.5 | 37.0 | |
| Embodiment 26 | 4.20 | 1.00 | 0.030 | 0.040 | -- | 0.003 | 0.08 | 80 | 918 | 1.67 | 35.5 | |
| Embodiment 27 | 4.20 | 1.00 | 0.310 | 0.390 | - | 0.002 | 0.18 | 950 | 928 | 1.67 | 35.5 | |
| Embodiment 28 | 2.21 | 0.53 | 0.030 | 0.025 | Mg0.20 | 0.002 | 0.11 | 122 | 720 | 1 | 41.5 | |
| Embodiment 29 | 3.32 | 0.86 | 0.050 | 0.022 | Zn0.15 Sn0.30 | 0.002 | 0.23 | 345 | 808 | 1.5 | 38.2 | |
| Embodiment 30 | 4.06 | 0.99 | 0.082 | 0.040 | Zn0.90 Sn0.50 Mg0.45 | 0.002 | 0.28 | 454 | 900 | 1.67 | 36.9 | |
| Comparative example 9 | 1.50 | 0.25 | 0.120 | 0.090 | - | 0.002 | 0.12 | 620 | 662 | 1 | 45.0 | |
| Comparative example 10 | 6.50 | 1.50 | 0.110 | 0.120 | - | Do not make sample | ||||||
| Comparative example 11 | 3.80 | 0.90 | 0.003 | 0.090 | - | 0.003 | 0.03 | 10 | 913 | 2 | 37.0 | |
| Comparative example 12 | 3.80 | 0.90 | 0.110 | 0.005 | - | 0.003 | 0.31 | 13 | 921 | 2 | 37.0 | |
| Comparative example 13 | 3.80 | 0.90 | 0.670 | 0.090 | - | 0.002 | 0.06 | 14 | 908 | 2.67 | 37.0 | |
| Comparative example 14 | 3.80 | 0.90 | 0.130 | 0.730 | - | 0.002 | 0.13 | 12 | 903 | 2.67 | 37.0 | |
Annotate: "-" do not add
(embodiment 4)
With method test the same with embodiment 1 and the every Albatra metal-of evaluation, this copper alloy contains 4.2 quality % nickel, 1.0 quality % silicon and element as shown in table 4 separately, and surplus is copper and unavoidable impurities.Production method is identical with embodiment 1 with measuring method.
As showing from result shown in the table 4, the tensile strength of the copper alloy of each embodiment of the present invention is 900MPa or more than the 900MPa, and R/t＜2.Yet on the contrary, the boron content of the copper alloy of comparative example 15 and the numbers of particles of X do not fall in the scope of the present invention's regulation with the ratio of the numbers of particles of Y.The manganese content of the copper alloy of comparative example 16 and the particle diameter of precipitate Y do not fall in the scope of the present invention's regulation.The particle diameter of the phosphorus content of the copper alloy of comparative example 17 and precipitate Y does not fall in the scope of the present invention's regulation.The manganese content of the copper alloy of comparative example 18 and the numbers of particles of X do not fall in the scope of the present invention's regulation with the ratio of the numbers of particles of Y.The phosphorus content that the copper alloy of comparative example 19 has, and the ratio of the numbers of particles of X and the numbers of particles of Y does not fall in the scope of the present invention's regulation.Therefore, the copper alloy of these comparative examples bending property separately is poor, and R/t is more than 2 or 2.
Table 4
| Element | The particle diameter μ m of X | The particle diameter μ m of Y | X numbers of particles/Y numbers of particles | Tensile strength MPa | Bending property R/t | Specific conductivity %IACS | ||||
| B quality % | Mn quality % | P quality % | Other quality % | |||||||
| Embodiment 31 | 0.050 | 0.100 | 0.100 | - | 0.003 | 0.13 | 150 | 904 | 1.67 | 35.5 |
| Embodiment 32 | 0.008 | 0.120 | 0.090 | - | 0.002 | 0.82 | 780 | 911 | 1.67 | 35.5 |
| Embodiment 33 | 0.094 | 0.080 | 0.110 | - | 0.003 | 0.08 | 1020 | 903 | 1.67 | 35.5 |
| Embodiment 34 | 0.050 | 0.020 | 0.030 | - | 0.003 | 0.09 | 180 | 908 | 1.67 | 35.5 |
| Embodiment 35 | 0.050 | 0.450 | 0.230 | - | 0.002 | 0.45 | 330 | 921 | 1.67 | 35.5 |
| Embodiment 36 | 0.055 | 0.025 | 0.025 | Sn0.30 | 0.003 | 0.54 | 234 | 902 | 1.67 | 35.2 |
| Embodiment 37 | 0.015 | 0.200 | 0.150 | Zn0.20 Mg0.08 | 0.002 | 0.67 | 332 | 901 | 1.67 | 34.2 |
| Embodiment 38 | 0.020 | 0.025 | 0.025 | Zn0.80 Sn0.60 Mg0.20 | 0.003 | 0.7 | 441 | 905 | 1.67 | 34.9 |
| Comparative example 15 | 0.500 | 0.120 | 0.090 | - | 0.002 | 0.45 | 11 | 921 | 2.67 | 35.5 |
| Comparative example 16 | 0.050 | 0.003 | 0.090 | - | 0.003 | 0.007 | 400 | 905 | 2.67 | 35.5 |
| Comparative example 17 | 0.050 | 0.110 | 0.005 | - | 0.003 | 0.005 | 580 | 913 | 3.3 | 35.5 |
| Comparative example 18 | 0.050 | 0.670 | 0.090 | - | 0.002 | 0.25 | 5 | 909 | 3.3 | 35.5 |
| Comparative example 19 | 0.050 | 0.130 | 0.730 | - | 0.002 | 0.7 | 8 | 915 | 2.67 | 35.5 |
Annotate: "-" do not add
(embodiment 5)
With method test the same with embodiment 1 and the every Albatra metal-of evaluation, this copper alloy contains nickel, silicon and antimony, and is as shown in table 5, and surplus is copper and unavoidable impurities, and measures its crystal grain diameter.Making method is identical with embodiment 1 with measuring method.The content that joins antimony in comparative example 28,29,30 and 31 is respectively 0.01 quality %, 1.0 quality %, 0.02 quality % and 1.2 quality %.Other copper alloy antimony amount separately is 0.1 quality %.
Measure crystal particle diameter according to JIS H 0501 (section method).Measure bending property by following method: being marked as " GW ", is to be that 10 millimeters and length are the test specimen of 25 millimeters sizes with cutting into width on each comfortable direction parallel with rolling direction of above-mentioned sample, and bending, and its bending axis is vertical with rolling direction; And, being marked as " BW ", is the size that sample is cut into separately abreast 10 millimeters of 25 millimeters of width and length with rolling direction, with GW in the same method bending, but bending axis is parallel with rolling direction, and according to GW in the same method assign to check by observing bend.
As showing from result shown in the table 5, the copper alloy of each embodiment of the present invention has fabulous performance.Yet with above-mentioned opposite, the copper alloy of comparative example 20 has very little nickel content, so it has the low precipitation precipitate X that separates out density, and tensile property is poor.The copper alloy of comparative example 21 has big nickel content, although therefore it is processed to pre-determined thickness, produces serious processing crack.Therefore, even checked the copper alloy structure of resulting sample in this comparative example 21, also can not check its performance.
The copper alloy of comparative example 22 has very little silicone content, so it has the low precipitate X that separates out density, and tensile property is poor.The copper alloy of comparative example 23 has too big silicone content, although therefore it is processed to final thickness, produces serious processing crack.Therefore, even checked the copper alloy structure of resulting sample in this comparative example 23, also can not check its performance.The copper alloy of comparative example 24 has the precipitate X of small particle size, and the copper alloy of comparative example 25 has the precipitate X of big particle diameter, and the copper alloy of comparative example 26 has the too low precipitate X that separates out density, so these copper alloys tensile property separately is poor.The silicone content of the copper alloy of comparative example 27 is big, so it has the precipitate X that height is separated out density, causes embrittlement.Although the copper alloy of comparative example 27 is processed to final thickness, produce serious processing crack.Therefore, even checked the copper alloy structure of resulting sample in this comparative example 27, also can not check its performance.The copper alloy of comparative example 28 has the precipitate Y of small particle size, the copper alloy of comparative example 29 has the precipitate Y of big particle diameter, and the copper alloy of comparative example 30 has the precipitate Y that separates out very much shallow lake density, so these copper alloys have very large crystal particle diameter separately, and its bending property is poor.The same alloy of comparative example 31 has the precipitate Y that height is separated out density, causes embrittlement.Although the copper alloy of comparative example 31 is processed to final thickness, produce serious processing crack.Therefore, even checked the copper alloy structure of resulting sample in this comparative example 31, also can not check its performance.
Table 5
| Element | Precipitate X | Precipitate Y | Crystal particle diameter μ m | Tensile strength MPa | Specific conductivity %IACS | Bending property GW R/t | Bending property BW R/t | ||||
| Ni quality % | Si quality % | Particle diameter μ m | Density/mm 2 | Particle diameter μ m | Density/mm 2 | ||||||
| Embodiment 39 | 3.8 | 0.9 | 0.025 | 6×10 10 | 0.210 | 3×10 5 | 8 | 830 | 35 | 1 | 1 |
| Embodiment 40 | 3.5 | 0.8 | 0.023 | 2×10 10 | 0.220 | 5×10 5 | 10 | 844 | 35 | 1 | 1 |
| Embodiment 41 | 4.2 | 1.2 | 0.026 | 2×10 11 | 0.230 | 7×10 5 | 9 | 908 | 32 | 1.5 | 1.5 |
| Embodiment 42 | 2.1 | 0.5 | 0.028 | 3×10 8 | 0.320 | 4×10 5 | 8 | 710 | 39 | 1 | 1 |
| Comparative example 20 | 1.8 | 0.5 | 0.024 | 7×10 7 | 0.300 | 3×10 5 | 11 | 610 | 45 | 1 | 1 |
| Comparative example 21 | 5.5 | 1.3 | 0.029 | 8×10 11 | 0.280 | 5×10 5 | 9 | Because the processing crack is energy measurement not | |||
| Comparative example 22 | 2 | 0.25 | 0.022 | 3×10 7 | 0.240 | 4×10 5 | 10 | 704 | 39 | 1 | 1 |
| Comparative example 23 | 5.2 | 1.9 | 0.029 | 9×10 11 | 0.310 | 7×10 5 | 12 | Because the processing crack is energy measurement not | |||
| Comparative example 24 | 3.5 | 0.8 | 0.0001 | 5×10 10 | 0.330 | 9×10 5 | 10 | 755 | 30 | 1 | 1 |
| Comparative example 25 | 3.6 | 0.8 | 0.112 | 6×10 10 | 0.290 | 7×10 5 | 9 | 789 | 37 | 1 | 1 |
| Comparative example 26 | 3 | 0.7 | 0.030 | 5×10 6 | 0.300 | 8×10 5 | 8 | 739 | 33 | 1 | 1 |
| Comparative example 27 | 4.8 | 1.55 | 0.028 | 4×10 13 | 0.280 | 3×10 5 | 10 | Because the processing crack is energy measurement not | |||
| Comparative example 28 | 3.9 | 0.8 | 0.033 | 5×10 10 | 0.008 | 7×10 5 | 40 | 829 | 35 | 3 | 4 |
| Comparative example 29 | 3.4 | 0.6 | 0.031 | 6×10 10 | 1.260 | 2×10 5 | 66 | 822 | 38 | 3 | 3 |
| Comparative example 30 | 3.6 | 0.7 | 0.029 | 3×10 10 | 0.330 | 7×10 3 | 26 | 840 | 35 | 2 | 2 |
| Comparative example 31 | 3.5 | 0.6 | 0.032 | 5×10 10 | 0.230 | 8×10 9 | 6 | Because the processing crack is energy measurement not | |||
(embodiment 6)
With method test the same with embodiment 5 and the every Albatra metal-of evaluation, this copper alloy contains just like table 6 and nickel shown below, silicon and chromium, and surplus is copper and unavoidable impurities.Making method is identical with embodiment 5 with measuring method.The content of chromium is respectively 0.005 quality %, 0.8 quality %, 0.01 quality % and 1.0 quality % in the comparative example 40,41,42 and 43.Other copper alloy chromium content separately is 0.05 quality %.
As showing from result shown in the table 6, the copper alloy of each embodiment of the present invention has fabulous performance.Yet with above-mentioned opposite, the copper alloy of comparative example 32 has very little nickel content, so it has the low precipitate X that separates out density, and its tensile property is poor.The copper alloy of comparative example 33 has big nickel content and silicone content, even therefore it is processed to final thickness, it also produces serious processing crack.Therefore, although checked the copper alloy structure of resulting sample in this comparative example 33, can not check its performance.The copper alloy of comparative example 34 has very little silicone content, so it has the low precipitate X that separates out density, and its tensile property is poor.The copper alloy of comparative example 35 has big silicone content, even therefore it is processed to final thickness, it also produces serious processing crack.Therefore, although checked the copper alloy structure of resulting sample in this comparative example 35, can not check its performance.The copper alloy of comparative example 36 has the precipitate X of small particle size, and the copper alloy of comparative example 37 has the precipitate X of big particle diameter, and the copper alloy of comparative example 38 has the too low precipitate X that separates out density, so these are used for the copper alloy of comparison, and tensile property is poor separately.The copper alloy of comparative example 39 has the precipitate X that height is separated out density, causes embrittlement.Even the copper alloy of comparative example 39 is processed to final thickness, it also produces serious processing crack.Therefore, although checked the copper alloy structure of resulting sample in this comparative example 39, can not check its performance.The copper alloy of comparative example 40 has the precipitate Y of small particle size, the copper alloy of comparative example 41 has the precipitate Y of big particle diameter, and the copper alloy of comparative example 42 has the too low precipitate Y that separates out density, so these copper alloys that are used for comparison have too big crystal particle diameter separately, and its bending property is poor.The copper alloy of comparative example 43 has the precipitate Y that height is separated out density, causes embrittlement.Even the copper alloy of comparative example 43 is processed to final thickness, it also produces serious processing crack.Therefore, although checked the copper alloy structure of resulting sample in this comparative example 43, can not check its performance.
Table 6
| Element | Precipitate X | Precipitate Y | Crystal particle diameter μ m | Tensile strength MPa | Specific conductivity %IACS | Bending property GW R/t | Bending property BW R/t | ||||
| Ni quality % | Si quality % | Particle diameter μ m | Density/mm 2 | Particle diameter μ m | Density/mm 2 | ||||||
| Embodiment 43 | 3.9 | 0.8 | 0.023 | 5×10 10 | 0.250 | 2×10 5 | 9 | 821 | 35 | 1 | 1 |
| Embodiment 44 | 3.7 | 0.8 | 0.020 | 3×10 10 | 0.290 | 4×10 5 | 12 | 856 | 35 | 1 | 1 |
| Embodiment 45 | 4.3 | 1.1 | 0.025 | 3×10 11 | 0.210 | 9×10 5 | 11 | 921 | 32 | 1.5 | 1.5 |
| Embodiment 46 | 2.3 | 0.6 | 0.029 | 4×10 8 | 0.300 | 5×10 5 | 9 | 709 | 40 | 1 | 1 |
| Comparative example 32 | 1.8 | 0.5 | 0.024 | 7×10 7 | 0.300 | 3×10 5 | 11 | 600 | 46 | 1 | 1 |
| Comparative example 33 | 5.5 | 1.57 | 0.022 | 9×10 11 | 0.220 | 6×10 5 | 9 | Because the processing crack is energy measurement not | |||
| Comparative example 34 | 2.1 | 0.25 | 0.028 | 4×10 7 | 0.250 | 5×10 5 | 13 | 640 | 38 | 1 | 1 |
| Comparative example 35 | 5.1 | 1.9 | 0.029 | 8×10 11 | 0.330 | 7×10 5 | 18 | Because the processing crack is energy measurement not | |||
| Comparative example 36 | 3.5 | 0.9 | 0.0005 | 6×10 10 | 0.380 | 8×10 5 | 14 | 779 | 32 | 1 | 1 |
| Comparative example 37 | 3.5 | 0.9 | 0.122 | 6×10 10 | 0.240 | 6×10 5 | 11 | 746 | 38 | 1 | 1 |
| Comparative example 38 | 3.1 | 0.8 | 0.028 | 7×10 6 | 0.320 | 5×10 5 | 13 | 756 | 31 | 1 | 1 |
| Comparative example 39 | 4.9 | 1.5 | 0.030 | 5×10 13 | 0.300 | 5×10 5 | 12 | Because the processing crack is energy measurement not | |||
| Comparative example 40 | 3.8 | 0.9 | 0.032 | 6×10 10 | 0.007 | 8×10 5 | 45 | 833 | 37 | 3 | 4 |
| Comparative example 41 | 3.5 | 0.7 | 0.034 | 7×10 10 | 1.330 | 3×10 5 | 54 | 850 | 35 | 3 | 3 |
| Comparative example 42 | 3.7 | 0.8 | 0.032 | 4×10 10 | 0.300 | 8×10 3 | 32 | 832 | 34 | 2 | 2 |
| Comparative example 43 | 3.4 | 0.8 | 0.035 | 4×10 10 | 0.200 | 9×10 9 | 5 | Because the processing crack is energy measurement not | |||
(embodiment 7)
To following all embodiment of the present invention, with the method test the same with embodiment 5 with evaluate copper alloy, this copper alloy contains 4.0 quality % nickel, 1.0 quality % silicon and element as shown in table 7 separately, surplus is copper and unavoidable impurities.Making method is identical with embodiment 5 with measuring method.The copper alloy of comparative example 44 contains 3.1 quality % nickel and 0.7 quality % silicon, the copper alloy of comparative example 45 contains 3.9 quality % nickel and 0.9 quality % silicon, and the copper alloy of comparative example 46 contains 4.9 quality % nickel and 1.2 quality % silicon, and surplus is copper and unavoidable impurities separately.
As showing from result shown in the table 8, the copper alloy of each embodiment of the present invention has fabulous performance.Yet with above-mentioned opposite, comparative example 44,45 and 46 copper alloy do not contain any precipitate Y separately, therefore have significantly big crystal particle diameter separately, and its bending property are poor.
Table 7
| The component that adds | Precipitate X | Precipitate Y | Crystal particle diameter μ m | Tensile strength MPa | Specific conductivity %IACS | Bending property GW R/t | Bending property BW R/t | |||
| Amount of element (quality %) | Particle diameter μ m | Density/mm 2 | Particle diameter μ m | Density/mm 2 | ||||||
| Embodiment 47 | Al0.1，As0.05 | 0.025 | 5×10 10 | 0.103 | 3×10 6 | 12 | 813 | 29 | 1.5 | 1.5 |
| Embodiment 48 | Al0.08，Hf0.09 | 0.024 | 4×10 10 | 0.400 | 2×10 7 | 11 | 814 | 28 | 1.5 | 1.5 |
| Embodiment 49 | Al0.07，Zr0.1 | 0.024 | 4×10 10 | 0.200 | 4×10 6 | 18 | 843 | 31 | 1.5 | 1.5 |
| Embodiment 50 | Cr0.03 | 0.023 | 6×10 10 | 0.340 | 4×10 6 | 15 | 812 | 33 | 1.5 | 1.5 |
| Embodiment 51 | Ti0.1，C0.03 | 0.014 | 5×10 11 | 0.980 | 2×10 4 | 18 | 836 | 39 | 1.5 | 1.5 |
| Embodiment 52 | Ti0.06，C0.02 | 0.024 | 4×10 10 | 0.760 | 1×10 4 | 13 | 834 | 38 | 1.5 | 1.5 |
| Embodiment 53 | Zr0.2 | 0.027 | 5×10 10 | 0.340 | 3×10 6 | 18 | 832 | 34 | 1.5 | 1.5 |
| Embodiment 54 | Cr0.3 | 0.026 | 6×10 10 | 0.550 | 3×10 6 | 14 | 824 | 35 | 1.5 | 1.5 |
| Embodiment 55 | Fe0.1，P0.05 | 0.028 | 3×10 10 | 0.220 | 3×10 6 | 10 | 856 | 35 | 1.5 | 1.5 |
| Embodiment 56 | Fe0.2，P0.05 | 0.018 | 7×10 10 | 0.120 | 3×10 7 | 9 | 812 | 39 | 1.5 | 1.5 |
| Embodiment 57 | Fe0.1，Zr0.1 | 0.025 | 7×10 10 | 0.450 | 7×10 5 | 8 | 822 | 35 | 1.5 | 1.5 |
| Embodiment 58 | In0.02 | 0.025 | 4×10 10 | 0.660 | 4×10 5 | 12 | 834 | 38 | 1.5 | 1.5 |
| Embodiment 59 | Mg0.1，Sb0.04 | 0.026 | 8×10 9 | 0.430 | 2×10 6 | 15 | 814 | 28 | 1.5 | 1.5 |
| Embodiment 60 | Mn0.2 | 0.018 | 6×10 10 | 0.400 | 7×10 5 | 11 | 808 | 31 | 1.5 | 1.5 |
| Embodiment 61 | Sb0.05 | 0.019 | 6×10 10 | 0.240 | 3×10 5 | 10 | 806 | 33 | 1.5 | 1.5 |
| Embodiment 62 | Ta0.1 | 0.027 | 3×10 10 | 0.430 | 2×10 6 | 8 | 842 | 37 | 1.5 | 1.5 |
| Embodiment 63 | V0.08，Zr0.08 | 0.026 | 3×10 10 | 0.840 | 9×10 5 | 13 | 813 | 36 | 1.5 | 1.5 |
| Comparative example 44 | - | 0.022 | 8×10 9 | Do not have | Do not have | 29 | 803 | 39 | 2 | 2 |
| Comparative example 45 | - | 0.025 | 4×10 10 | Do not have | Do not have | 30 | 823 | 36 | 3 | 3 |
| Comparative example 46 | - | 0.029 | 8×10 9 | Do not have | Do not have | 33 | 890 | 32 | 4 | 3 |
Annotate: "-" do not add
(embodiment 8)
With method test the same with embodiment 5 and evaluation copper alloy, this copper alloy contains nickel as shown in table 8, silicon, tin, zinc, magnesium elements separately, and surplus is copper and unavoidable impurities.Making method is identical with embodiment 5 with measuring method.
As showing from result shown in the table 7, the copper alloy of each embodiment of the present invention all has fabulous performance.Yet with above-mentioned opposite, comparative example 47,48,49 and 50 copper alloy do not contain any precipitate Y separately, therefore have significantly big crystal particle diameter separately, and its bending property are poor.
Table 8
| Element (quality %) | Precipitate X | Precipitate Y | Crystal particle diameter μ m | Tensile strength MPa | Specific conductivity %IACS | Bending property GW R/t | Bending property BW R/t | ||||||||
| Ni | Si | Sn | Zn | Mg | Other | Particle diameter μ m | Density/mm 2 | Particle diameter μ m | Density/mm 2 | ||||||
| Embodiment 64 | 3 | 0.8 | 0.1 | 0.5 | 0.1 | Sb0.08 | 0.025 | 2×10 10 | 0.200 | 2×10 6 | 12 | 811 | 37 | 0.75 | 0.5 |
| Embodiment 65 | 3.5 | 0.9 | 0.024 | 6×10 10 | 0.325 | 3×10 6 | 11 | 842 | 35 | 0.75 | 0.75 | ||||
| Embodiment 66 | 4 | 1.1 | 0.024 | 4×10 10 | 0.250 | 3×10 6 | 18 | 865 | 33 | 1 | 1 | ||||
| Embodiment 67 | 4.5 | 1.3 | 0.023 | 9×10 10 | 0.230 | 4×10 6 | 15 | 891 | 31 | 1.5 | 1.5 | ||||
| Embodiment 68 | 3 | 0.8 | 0.1 | 0.5 | 0.1 | Cr0.04 | 0.026 | 2×10 10 | 0.150 | 4×10 5 | 12 | 805 | 36 | 0.75 | 0.5 |
| Embodiment 69 | 3.5 | 0.9 | 0.014 | 6×10 10 | 0.230 | 3×10 5 | 18 | 839 | 34 | 0.75 | 0.75 | ||||
| Embodiment 70 | 4 | 1.1 | 0.024 | 9×10 10 | 0.190 | 4×10 5 | 13 | 855 | 32 | 1 | 1 | ||||
| Embodiment 71 | 4.5 | 1.3 | 0.027 | 1×10 11 | 0.340 | 4×10 5 | 18 | 888 | 30 | 1.5 | 1.5 | ||||
| Embodiment 72 | 3 | 0.8 | 0.1 | 0.5 | 0.1 | Zr0.2 | 0.026 | 4×10 10 | 0.150 | 9×10 6 | 14 | 810 | 38 | 0.75 | 0.5 |
| Embodiment 73 | 3.5 | 0.9 | 0.028 | 7×10 10 | 0.280 | 8×10 6 | 10 | 836 | 36 | 0.75 | 0.75 | ||||
| Embodiment 74 | 4 | 1.1 | 0.018 | 9×10 10 | 0.190 | 1×10 7 | 9 | 856 | 33 | 1 | 1 | ||||
| Embodiment 75 | 4.5 | 1.3 | 0.025 | 2×10 11 | 0.120 | 7×10 6 | 8 | 891 | 32 | 1.5 | 1.5 | ||||
| Comparative example 47 | 3 | 0.8 | 0.1 | 0.5 | 0.1 | - | 0.022 | 2×10 10 | Do not have | Do not have | 29 | 805 | 37 | 2 | 1.5 |
| Comparative example 48 | 3.5 | 0.9 | - | 0.025 | 5×10 10 | Do not have | Do not have | 30 | 835 | 35 | 2 | 3 | |||
| Comparative example 49 | 4 | 1.1 | - | 0.023 | 8×10 10 | Do not have | Do not have | 39 | 866 | 33 | 3 | 3 | |||
| Comparative example 50 | 4.5 | 1.3 | - | 0.029 | 2×10 11 | Do not have | Do not have | 33 | 880 | 30 | 4 | 4 | |||
Annotate: "-" do not add
Industrial applicibility
Copper alloy of the present invention can be preferably applied to lead frame, junctor or the terminal material of Electrical and Electronic apparatus and element, for example automotive connector/terminal material, rly. and switch.
Though described and our at present concrete relevant invention of scheme, we are intended that any details that the present invention is not limited to specification sheets, unless otherwise mentioned, but are interpreted as widely in the spirit and scope that appended claims states.
Claims (19)
1. an Albatra metal-comprises:
The precipitate X that forms by nickel and silicon; With
Comprise nickel or silicon or neither comprise the precipitate Y that nickel does not comprise silicon again,
Wherein the particle diameter of precipitate X is 0.001 to 0.1 μ m, and the particle diameter of precipitate Y is 0.01 to 1 μ m.
2. the copper alloy of claim 1, wherein the fusing point of precipitate Y is higher than solid solution temperature.
3. the copper alloy of claim 2, it comprises the nickel of 2 to 5 quality %, the silicon of 0.3 to 1.5 quality % and the boron of 0.005 to 0.1 quality %, surplus is copper and unavoidable impurities, during wherein the numbers of particles of precipitate X is every square millimeter in every square millimeter 20 to 2,000 times of the numbers of particles of precipitate Y.
4. the copper alloy of claim 3, wherein the numbers of particles of precipitate X is every square millimeter 10
8To 10
12Individual, and the numbers of particles of precipitate Y is every square millimeter 10
4To 10
8Individual.
5. the copper alloy of claim 4, it comprises at least a element in aluminium, arsenic, hafnium, zirconium, chromium, titanium, carbon, iron, phosphorus, indium, calcium halophosphate activated by antimony andmanganese, tantalum and the vanadium of being selected from of 0.005 to 0.5 quality %.
6. the copper alloy of claim 5, wherein precipitate Y is by at least a composition the in aluminium-arsenic, aluminium-hafnium, aluminum-zirconium, aluminium-chromium, titanium-carbon, copper-titanium, copper-zirconium, chromium-silicon, iron-phosphorus, iron-silicon, iron-zirconium, indium-nickel, magnesium-calcium halophosphate activated by antimony andmanganese-silicon, nickel-antimony, silicon-tantalum and the vanadium-zirconium.
7. the copper alloy of claim 6, it also comprises at least a element in the magnesium of the zinc of the tin that is selected from 0.1 to 1.0 quality %, 0.1 to 1.0 quality % and 0.05 to 0.5 quality %.
8. the copper alloy of claim 7, it is used for electric or electric mechanical and instrument apparatus and element.
9. the copper alloy of claim 2, it comprises the nickel of 2 to 5 quality %, the silicon of 0.3 to 1.5 quality %, the manganese of 0.01 to 0.5 quality % and the phosphorus of 0.01 to 0.5 quality %, surplus is copper and unavoidable impurities, during wherein the numbers of particles of precipitate X is every square millimeter in every square millimeter 20 to 2,000 times of the numbers of particles of precipitate Y.
10. the copper alloy of claim 9, wherein the numbers of particles of precipitate X is every square millimeter 10
8To 10
12Individual, and the numbers of particles of precipitate Y is every square millimeter 10
4To 10
8Individual.
11. the copper alloy of claim 10, it comprises at least a element in aluminium, arsenic, hafnium, zirconium, chromium, titanium, carbon, iron, phosphorus, indium, calcium halophosphate activated by antimony andmanganese, tantalum and the vanadium of being selected from of 0.005 to 0.5 quality %.
12. the copper alloy of claim 11, wherein precipitate Y is by at least a composition the in aluminium-arsenic, aluminium-hafnium, aluminum-zirconium, aluminium-chromium, titanium-carbon, copper-titanium, copper-zirconium, chromium-silicon, iron-phosphorus, iron-silicon, iron-zirconium, indium-nickel, magnesium-calcium halophosphate activated by antimony andmanganese-silicon, nickel-antimony, silicon-tantalum and the vanadium-zirconium.
13. the copper alloy of claim 12, it also comprises at least a element in the magnesium of the zinc of the tin that is selected from 0.1 to 1.0 quality %, 0.1 to 1.0 quality % and 0.05 to 0.5 quality %.
14. the copper alloy of claim 13, it is used for electric or electronic equipments and element.
15. the copper alloy of claim 2, it comprises the nickel of 2 to 5 quality %, the silicon of 0.3 to 1.5 quality %, the boron of 0.005 to 0.1 quality %, the manganese of 0.01 to 0.5 quality % and the phosphorus of 0.01 to 0.5 quality %, surplus is copper and unavoidable impurities, during wherein the numbers of particles of precipitate X is every square millimeter in every square millimeter 20 to 2,000 times of the numbers of particles of precipitate Y.
16. the copper alloy of claim 15, wherein the numbers of particles of precipitate X is every square millimeter 10
8To 10
12Individual, and the numbers of particles of precipitate Y is every square millimeter 10
4To 10
8Individual.
17. the copper alloy of claim 16, it comprises at least a element in aluminium, arsenic, hafnium, zirconium, chromium, titanium, carbon, iron, phosphorus, indium, calcium halophosphate activated by antimony andmanganese, tantalum and the vanadium of being selected from of 0.005 to 0.5 quality %.
18. the copper alloy of claim 17, wherein precipitate Y is by at least a composition the in aluminium-arsenic, aluminium-hafnium, aluminum-zirconium, aluminium-chromium, titanium-carbon, copper-titanium, copper-zirconium, chromium-silicon, iron-phosphorus, iron-silicon, iron-zirconium, indium-nickel, magnesium-calcium halophosphate activated by antimony andmanganese-silicon, nickel-antimony, silicon-tantalum and the vanadium-zirconium.
19. the copper alloy of claim 18, it is used for electric or electronic equipments and element.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP054905/2004 | 2004-02-27 | ||
| JP2004054905 | 2004-02-27 | ||
| JP328249/2004 | 2004-11-11 |
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|---|---|
| CN1926253A true CN1926253A (en) | 2007-03-07 |
| CN100545282C CN100545282C (en) | 2009-09-30 |
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Cited By (6)
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|---|---|---|---|---|
| CN102105611A (en) * | 2009-04-30 | 2011-06-22 | Jx日矿日石金属株式会社 | Cu-Ni-Si-Mg-based alloy having improved electrical conductivity and bendability |
| CN103680671A (en) * | 2013-12-14 | 2014-03-26 | 苏州戴尔曼电器有限公司 | Copper and iron nickel alloy cable strong in bending resisting performance |
| CN104372200A (en) * | 2014-11-14 | 2015-02-25 | 无锡阳工机械制造有限公司 | Brine-corrosion-resistant alloy |
| CN104894429A (en) * | 2015-06-25 | 2015-09-09 | 潘应生 | Chromium-copper alloy and preparation method thereof |
| CN109971993A (en) * | 2017-12-28 | 2019-07-05 | 北京有色金属研究总院 | A kind of high Vulcan metal and preparation method thereof |
| CN110234796A (en) * | 2017-02-03 | 2019-09-13 | 日产自动车株式会社 | Sliding component and sliding component for internal combustion engine |
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2005
- 2005-02-25 CN CNB2005800063298A patent/CN100545282C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102105611A (en) * | 2009-04-30 | 2011-06-22 | Jx日矿日石金属株式会社 | Cu-Ni-Si-Mg-based alloy having improved electrical conductivity and bendability |
| CN103680671A (en) * | 2013-12-14 | 2014-03-26 | 苏州戴尔曼电器有限公司 | Copper and iron nickel alloy cable strong in bending resisting performance |
| CN104372200A (en) * | 2014-11-14 | 2015-02-25 | 无锡阳工机械制造有限公司 | Brine-corrosion-resistant alloy |
| CN104894429A (en) * | 2015-06-25 | 2015-09-09 | 潘应生 | Chromium-copper alloy and preparation method thereof |
| CN110234796A (en) * | 2017-02-03 | 2019-09-13 | 日产自动车株式会社 | Sliding component and sliding component for internal combustion engine |
| US20200011211A1 (en) * | 2017-02-03 | 2020-01-09 | Nissan Motor Co., Ltd. | Sliding member, and sliding member for internal combustion engine |
| US10927893B2 (en) | 2017-02-03 | 2021-02-23 | Nissan Motor Co., Ltd. | Sliding member, and sliding member for internal combustion engine |
| CN109971993A (en) * | 2017-12-28 | 2019-07-05 | 北京有色金属研究总院 | A kind of high Vulcan metal and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100545282C (en) | 2009-09-30 |
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