CN103924118A - Copper Alloy Material, Power Distribution Component For Electric Automobile, And Power Distribution Component For Hybrid Power Automobile - Google Patents
Copper Alloy Material, Power Distribution Component For Electric Automobile, And Power Distribution Component For Hybrid Power Automobile Download PDFInfo
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- CN103924118A CN103924118A CN201310723755.XA CN201310723755A CN103924118A CN 103924118 A CN103924118 A CN 103924118A CN 201310723755 A CN201310723755 A CN 201310723755A CN 103924118 A CN103924118 A CN 103924118A
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 122
- 239000000956 alloy Substances 0.000 title claims abstract description 98
- 238000009826 distribution Methods 0.000 title claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000001301 oxygen Substances 0.000 claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims description 52
- 230000000116 mitigating effect Effects 0.000 claims description 18
- 235000019589 hardness Nutrition 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 25
- 230000035882 stress Effects 0.000 description 22
- 238000005097 cold rolling Methods 0.000 description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 239000010949 copper Substances 0.000 description 14
- 229910052802 copper Inorganic materials 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000005266 casting Methods 0.000 description 9
- 229910052709 silver Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000007669 thermal treatment Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- 238000005098 hot rolling Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000012795 verification Methods 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000009429 distress Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The invention provides a copper alloy material, a power distribution component for an electric automobile, and a power distribution component for a hybrid power automobile. The copper alloy material sustains high electric conductivity and simultaneously improves heat resistance. The copper alloy material at least comprises the components of: more than 0.003wt% and less than 0.01wt% of Zr, and more than 0.03wt% and less than 0.1wt% of Ag, wherein the content of oxygen is less than 0.001wt%; the electric conductivity is above 95%IACS, and Vickers-hardness is above 120Hv.
Description
Technical field
The present invention relates to Cu alloy material, when particularly maintaining high conductivity, there is excellent stable on heating Cu alloy material.
Background technology
In the past, material of, electronic unit electric as such as semiconductor lead frame, bonder terminal etc. etc., was widely used Cu alloy material.In recent years, such Cu alloy material also uses sometimes in the parts of the stream super-high-currents such as the power distribution unit of such as electromobile, hybrid vehicle.Therefore, require to have high conductivity for Cu alloy material.
In addition, at Cu alloy material, for such as electromobile etc. in the situation that, Cu alloy material majority uses under the harsh environment being exposed to for a long time in comparatively high temps.Therefore, even intensity does not also reduce and maintains high reliability while requiring to use under so harsh environment for Cu alloy material., require to have thermotolerance for Cu alloy material.
Usually used as the Cu alloy material with high conductivity, for example, propose to use the Cu alloy material that there is the tough pitch copper (C1100), oxygen free copper (C1020) of excellent electroconductibility and heat conductivity and form.Such Cu alloy material has the electric conductivity of 100%IACS left and right.But the thermotolerance of this Cu alloy material that has used tough pitch copper, oxygen free copper is low, therefore, if used, has the situation of strength decreased under above-mentioned severe rugged environment.
Therefore, proposed to improve intensity, improve stable on heating Cu alloy material by adding for example a small amount of tin (Sn), a small amount of iron (Fe), a small amount of zirconium (Zr).The copper alloy (C1510) that, proposed to use the copper alloy (C1441) that contains a small amount of tin (Sn), the copper alloy (C1921) that contains a small amount of iron (Fe), contains a small amount of zirconium (Zr) etc. and the Cu alloy material (for example, with reference to patent documentation 1～4) that forms.
Prior art document
Patent documentation
Patent documentation 1: No. 4495251 communique of Japanese Patent
Patent documentation 2: Japanese kokai publication hei 9-118943 communique
Patent documentation 3: TOHKEMY 2008-248275 communique
Patent documentation 4: TOHKEMY 2007-92176 communique
Summary of the invention
The problem that invention will solve
But although the Cu alloy material that has for example added a small amount of Fe etc. above-mentioned has excellent thermotolerance, most electric conductivity is reduced to 90%IACS left and right.Therefore, such Cu alloy material is difficult to sometimes as the distribution component etc. of such as electromobile that need to flow super-high-current.In addition, if consider the desired environments for use such as electromobile in recent years, require the further reliability in high-temperature region for Cu alloy material, i.e. further high thermotolerance.
Therefore, the object of the invention is to, solve above-mentioned problem, a kind of stable on heating Cu alloy material that further improved when maintaining high conductivity is provided.
The method of dealing with problems
In order to solve above-mentioned problem, the present invention forms as follows.
According to the 1st embodiment of the present invention, a kind of Cu alloy material is provided, the Ag more than Zr more than it at least contains 0.003 quality % and below 0.01 quality % and 0.03 quality % and below 0.1 quality %, the content of oxygen is below 0.001 quality %, electric conductivity is more than 95%IACS, and Vickers' hardness is more than 120Hv.
According to the 2nd embodiment of the present invention, the Cu alloy material of the 1st embodiment is provided, its electric conductivity is more than 97%IACS.
According to the 3rd embodiment of the present invention, provide the 1st or the Cu alloy material of the 2nd embodiment, the Vickers' hardnesses 400 DEG C of heating after 5 minutes are more than 100Hv.
According to the 4th embodiment of the present invention, the Cu alloy material of any one in the 1st to the 3rd embodiment is provided, the Vickers' hardness 450 DEG C of heating after 5 minutes is more than 98Hv.
According to the 5th embodiment of the present invention, the Cu alloy material of any one in the 1st to the 4th embodiment is provided, the stress mitigation rate 150 DEG C of heating after 1000 hours is below 30%.
According to the 6th embodiment of the present invention, a kind of power distribution unit used for electric vehicle is provided, use the Cu alloy material of any one in the 1st to the 5th embodiment and form.
According to the 7th embodiment of the present invention, a kind of power distribution unit of Hybrid Vehicle is provided, use the Cu alloy material of any one in the 1st to the 5th embodiment and form.
The effect of invention
According to Cu alloy material of the present invention, power distribution unit used for electric vehicle and the power distribution unit of Hybrid Vehicle, can in maintaining high electric conductivity, further improve thermotolerance.
Embodiment
Below an embodiment of Cu alloy material of the present invention is described.
(1) formation of Cu alloy material
Silver (Ag) more than the zirconium (Zr) more than the Cu alloy material of present embodiment at least contains 0.003 quality % and below 0.01 quality % and 0.03 quality % and below 0.1 quality %., use taking copper (Cu) as mother metal the copper alloy of the Zr be at least added with 0.003 quality % in its mother metal more than and below 0.01 quality % and the Ag more than 0.03 quality % and below 0.1 quality % and form Cu alloy material.Thus, in the high conductivity (excellent electroconductibility) of Cu alloy material more than maintaining 95%IACS, there is excellent thermotolerance.That is, by utilizing the interaction between Zr and Ag composition, thereby the reduction of electric conductivity can be suppressed to inferior limit, improve thermotolerance simultaneously.
Therefore, the Cu alloy material of present embodiment can be aptly for being exposed to for a long time under the severe rugged environment of comparatively high temps, stream super-high-current and the power distribution unit of such as electromobile, the hybrid vehicle etc. that use.Such power distribution unit can flow super-high-current, even if also can inhibition strength reduce in the case of the temperature rise of power distribution unit simultaneously.
Can improve thermotolerance although only contain the Cu alloy material of Zr, can not avoid electric conductivity to reduce, have the situation that is difficult to maintain high conductivity.
The Cu alloy material that only contains Ag can be expected stable on heating raising in the reduction that suppresses electric conductivity.But, due to Ag high price, therefore, in order to suppress the rising of manufacturing cost, content need to be suppressed to trace.Therefore,, only containing in the Cu alloy material of Ag, have and can not bring up to desirable stable on heating situation.
If the content of Zr is less than 0.003 quality %, stable on heating raising effect is low, has and can not obtain desirable stable on heating situation.If the content of Zr exceedes 0.01 quality %, although can obtain desirable thermotolerance, the situation that has electric conductivity to reduce., Cu alloy material has the situation that is difficult to maintain high conductivity more than 95%IACS.Especially, preferably the content of Zr is more than 0.003 quality % and below 0.006 quality %, in this case, is easy to obtain good electric conductivity.
If the content of Ag is less than 0.03 quality %, similarly stable on heating raising effect is low with the situation of above-mentioned Zr, has and can not obtain desirable stable on heating situation.If the content of Ag exceedes 0.1 quality %, electric conductivity reduces, and has the situation that is difficult to maintain electric conductivity more than 95%IACS.In addition, if the addition of the Ag of high price increases, manufacturing cost rises.Especially, preferably the content of Ag is more than 0.03 quality % and below 0.06 quality %, in this case, is easy to obtain good characteristic and the balance of manufacturing cost.
The content of the oxygen (O) in Cu alloy material is below 0.001 quality %.As the major cause of the stable on heating raising effect that hinders Zr, Ag to have, can be set forth in the existence of the oxygen containing in Cu alloy material.The oxygen containing in Cu alloy material reacts with Zr, Ag and forms oxide compound.Particularly Zr easily reacts with oxygen and forms oxide compound (ZrO
2).If Zr becomes oxide compound, improve stable on heating effect and significantly reduce.Therefore,, in the Cu alloy material of present embodiment, the content of oxygen is adjusted into below 0.001 quality %.Thus, can further bring into play and contain the stable on heating raising effect that Zr and Ag bring.Therefore, the content of Zr and Ag can be suppressed for inferior limit, thereby can suppress the reduction of electric conductivity.Consequently, Cu alloy material can improve thermotolerance in maintaining high conductivity.
If the content of oxygen exceedes 0.001 quality %, have and cannot obtain desirable stable on heating situation.That is, particularly form oxide compound and can make energy waste become large because Zr reacts with oxygen, therefore have and can not improve fully stable on heating situation.
As described later, when manufactured copper alloy material, repeatedly carry out cold-rolling treatment and the thermal treatment of stipulated number.Conventionally, if carry out cold-rolling treatment, the hardness of Cu alloy material increases, but electric conductivity reduces.At this moment,, by setting as described above at least Zr and the content of Ag and the content of oxygen, in can making the electric conductivity of Cu alloy material more than maintaining 95%IACS, more than preferred 97%IACS, it is more than 120Hv making Vickers' hardness.That is, though Cu alloy material be hardened to by cold-rolling treatment Vickers' hardness be more than 120Hv after, also can maintain that 95%IACS is above, preferred high conductivity more than 97%IACS.
On the other hand, for example add tin (Sn), iron (Fe) etc. passing through in the past and make in Cu alloy material that thermotolerance improves, in distress to be hardened to Vickers' hardness be that electric conductivity behind 120Hv left and right is situation more than 95%IACS.
Here, for reference, for example using the electric conductivity under Cu alloy material that tough pitch copper, oxygen free copper the form soft state after thermal treatment is 102%IACS left and right, and being hardened to Vickers' hardness by cold-rolling treatment is that electric conductivity behind 120Hv left and right is 100%IACS left and right.
In addition, 400 DEG C of heating, the Vickers' hardness after 5 minutes is more than 100Hv to the Cu alloy material of present embodiment.Vickers' hardness 450 DEG C of heating after 5 minutes can be more than 98Hv.Be to there is excellent thermotolerance in the Cu alloy material of the present embodiment high conductivity more than maintaining 95%IACS.On the other hand, for example using in the Cu alloy material that tough pitch copper, oxygen free copper form in the past, if about 300 DEG C heating 5 minutes, have to produce and soften and make the significantly reduced situation of Vickers' hardness.
In addition, 150 DEG C of heating, the stress mitigation rate after 1000 hours is below 30% to the Cu alloy material of present embodiment., the Cu alloy material of present embodiment considers also to have excellent thermotolerance from the viewpoint of stress mitigation rate.In addition, stress mitigation rate is the value of measuring by the socle girder mode of NEC material industry meeting standard specifications EMAS-1011 and the Japanese Shen Tong technological standard JCBA-T309 of association defined.
As mentioned above, the Cu alloy material of present embodiment has excellent thermotolerance in maintaining high electric conductivity.Therefore,, even, also can inhibition strength reduce using in the case of being exposed to for a long time the dirty super-high-current of severe rugged environment in comparatively high temps, guarantee sufficient reliability.Consequently, the Cu alloy material of present embodiment can be aptly for power distribution unit in such as electromobile, hybrid vehicle etc.
(2) manufacture method of Cu alloy material
Below, an embodiment of the manufacture method of the Cu alloy material to present embodiment describes.
The casting process of copper alloy
In the manufacture method of the Cu alloy material of present embodiment, first casting has the copper alloy of composition requirement., first use such as high frequency melting furnace etc. to manufacture liquation as copper (Cu) fusing of mother metal.In this liquation, the silver (Ag) more than the zirconium (Zr) more than adding 0.003 quality % and below 0.01 quality % and 0.03 quality % and below 0.1 quality %, thereby the liquation of formation copper alloy.At this moment be, that mode below 0.001 quality % is adjusted according to the content that makes the oxygen (O) in the liquation of copper alloy.Then, the liquation of this copper alloy be supplied to mold and manufacture the ingot casting of regulation shape.It should be noted that, the oxygen partial pressure in the atmosphere when adjustment of above-mentioned oxygen level can be made liquation by adjustment is controlled, and in the time that need reduce oxygen level, can control by for example sneak into the reducing gas such as carbon monoxide, hydrogen in atmosphere.
Hot-rolled process
After casting process finishes, by for example casting rolling mode continuously, the ingot casting of casting is heated to specified temperature (for example 950 DEG C) and carries out hot rolling processing, form the copper alloy plate of specific thickness.After hot rolling finishes, can be as soon as possible that copper alloy plate is cooling.
Cold rolling, heat treatment step
After hot rolling processing finishes, the sheet material of copper alloy is carried out to cold-rolling treatment and the thermal treatment (anneal) that is heated to specified temperature (for example 700 DEG C), form the Cu alloy material of specific thickness.Cold-rolling treatment and thermal treatment can be carried out respectively stipulated number repeatedly.At this moment, can for example, under the degree of finish (60%) of regulation, carry out final cold-rolling treatment.If the degree of finish of final cold-rolling treatment is too high, Cu alloy material is easily accumulated strain.Because this strain becomes the energy source that stress relaxes, if therefore to Cu alloy material heating (Cu alloy material becomes high temperature), there is the stress of generation to relax, the situation that intensity easily reduces.The situation that, has the thermotolerance of Cu alloy material to reduce.In addition, can respectively carry out 1 cold-rolling treatment and thermal treatment.Thermal treatment can be batch process, can be also continuous processing.Thus, can manufacture the Cu alloy material of present embodiment, finish its manufacturing process.
(3) effect of present embodiment
According to present embodiment, there are one or more effects shown below.
(a) according to present embodiment, the Ag more than Zr more than Cu alloy material at least contains 0.003 quality % and below 0.01 quality % and 0.03 quality % and below 0.1 quality %.In addition, the content of the oxygen in Cu alloy material (O) is adjusted into below 0.001 quality %.Thus, Cu alloy material can improve thermotolerance in maintaining high conductivity.That is, Cu alloy material maintain with the high conductivity that uses fine copper as the Cu alloy material equal extent of mother metal in, even if there is the excellent heat resistance that at high temperature also can not cause strength decreased.That is, can maintain electric conductivity more than above, the preferred 97%IACS of 95%IACS, it is more than 120Hv making Vickers' hardness simultaneously.Therefore, the Cu alloy material of present embodiment can use under the severe rugged environment being exposed to for a long time in comparatively high temps, can be used as aptly the power distribution unit of such as electromobile, the hybrid vehicle etc. of stream super-high-current.For example, in the such as power supply module of reliability that in addition, can be under the various environment of needs etc., use.
(b), according to present embodiment, 400 DEG C of heating, the Vickers' hardness after 5 minutes is more than 100Hv to Cu alloy material.Preferably 450 DEG C of heating, the Vickers' hardness after 5 minutes is more than 98Hv., the Cu alloy material of present embodiment can have excellent thermotolerance in the high conductivity more than maintaining 95%IACS.
(c), according to present embodiment, 150 DEG C of heating, the stress mitigation rate after 1000 hours is below 30% to Cu alloy material., the Cu alloy material of present embodiment considers also have excellent thermotolerance from the viewpoint of stress mitigation rate.
Embodiment
The following describes embodiments of the invention, but the invention is not restricted to these embodiment.
Embodiment 1
In embodiment 1, use oxygen free copper as mother metal.Then, use high frequency melting furnace, under nitrogen atmosphere, melt oxygen free copper and make (melting) liquation.Under nitrogen atmosphere, in this liquation, add the zirconium (Zr) of 0.004 quality %, the silver (Ag) of 0.05 quality %, make the liquation of copper alloy.Afterwards, the liquation of the copper alloy of making is supplied to mold, the ingot casting of cast thickness 25mm, width 30mm, length 150mm.
At the temperature (950 DEG C) of regulation, this ingot casting is heated and carries out hot rolling processing, the copper alloy plate that making thickness is 8mm.Then, the copper alloy plate that is 8mm to thickness carries out cold-rolling treatment and makes the sheet material that thickness is the copper alloy of 0.5mm, and the copper alloy plate that is 0.5mm to thickness carries out the thermal treatment (anneal) of 1 minute at 700 DEG C.Afterwards, under 60% degree of finish, carry out final cold-rolling treatment, the Cu alloy material that making thickness is 0.2mm.Set it as the sample of embodiment 1.
Embodiment 2～8 and comparative example 1～10
In embodiment 2～8 and comparative example 1～10, the Zr adding in the liquation of copper alloy and the addition of Ag are as shown in table 1.Other and the above embodiments 1 similarly operate and make Cu alloy material.Using them respectively as the sample of embodiment 2～8 and comparative example 1～10.
To the embodiment 1～8 making as described above and each sample of comparative example 1～10, analyze the content of oxygen (O).The results are shown in table 1.
Table 1
As described in Table 1, any the content of oxygen of each sample that confirms embodiment 1～8 and comparative example 1～10 is below 0.001 quality %.
To the embodiment 1～8 making as described above and each sample of comparative example 1～10, measure respectively the Vickers' hardness before electric conductivity, heating, the Vickers' hardness 400 DEG C of heating after 5 minutes, the Vickers' hardness 450 DEG C of heating after 5 minutes, the stress mitigation rate 150 DEG C of heating after 1000 hours.The results are shown in table 2.
The mensuration of stress mitigation rate is used the socle girder mode of NEC material industry meeting standard specifications EMAS-1011 and the Japanese Shen Tong technological standard JCBA-T309 of association defined and carries out., first cut out the test film of prescribed level from each sample.Make each test film form the state of socle girder and remain on testing table, apply as the stress in bending (the surperficial maximum stress at initial stage) of 80% value of 0.2% yield strength value and be used as load.Measure the deflection (initial stage deflection) producing on test film at this moment.Under to the state of test film applying load, for example, in for example heating arrangements (baking oven) that each test film is heated to 150 DEG C, keep 1000 hours.Afterwards, take out test film from heating arrangements, the permanent strain (deflection being produced by tension set) while measuring unloading stress in bending.Then, calculate stress mitigation rate by the formula of stress mitigation rate=(deflection/initial stage deflection being produced by tension set) × 100.
Table 2
Record as table 2, the electric conductivity that confirms the sample of embodiment 1 is 97.9%IACS, and the Vickers' hardness before heating is 126Hv.The sample that, confirms embodiment 1 has maintained high conductivity more than 97%IACS under the state being hardened to by cold-rolling treatment after Vickers' hardness is 126Hv.Thus, the sample that confirms embodiment 1 has and uses the high conductivity of the Cu alloy material equal extent that fine copper forms as mother metal.
In addition, 400 DEG C of heating, the Vickers' hardnesses after 5 minutes are 114Hv to the sample that confirms embodiment 1, Vickers' hardnesses 450 DEG C of heating after 5 minutes are 110Hv., after 5 minutes, also maintained Vickers' hardness more than 100Hv 450 DEG C of heating even if confirm the sample of embodiment 1.In addition, the stress mitigation rate that confirms the sample of embodiment 1 is 20.4%, has maintained the value below 30%.There is good thermotolerance by these results verifications to the sample of embodiment 1.
Confirm embodiment 2～8 each sample any be to have maintained electric conductivity more than 95%IACS under the state after more than 120Hv be hardened to Vickers' hardness by cold-rolling treatment.The sample that confirms the embodiment 4～5 of the addition less amount that particularly makes Zr has maintained high conductivity more than 97%IACS.
Confirm embodiment 2～8 each sample any all maintained Vickers' hardness more than 100Hv 400 DEG C of heating after 5 minutes.The sample that confirms the more embodiment 6～8 of addition that particularly makes Zr has also maintained Vickers' hardness more than 100Hv 450 DEG C of heating after 5 minutes., confirm embodiment 2～8 each sample any all there is more excellent thermotolerance.
In addition, any the stress mitigation rate of each sample that confirms embodiment 2～8 is all suppressed in below 30%, also has excellent thermotolerance from the viewpoint of stress mitigation rate.
By above results verification, to each sample of embodiment 1～8, any all has high conductivity and excellent thermotolerance concurrently.
Confirm: do not add Zr and only added each sample that each sample of comparative example 1～2 of Ag and the addition of Zr are less than the comparative example 3～4 of 0.003 quality %, poor heat resistance compared with each sample of embodiment 1～8.That is, confirm: each sample of comparative example 1～4 softens in the time heating 5 minutes for 400 DEG C, thereby makes Vickers' hardness be significantly less than 100Hv.
Confirm: have excellent thermotolerance although the addition of Zr exceedes compared with each sample of comparative example 5～7 of 0.1 quality % and each sample of embodiment 1～8, the reduction of electric conductivity is large, can not maintain electric conductivity more than 95%IACS.
Confirm: do not add Ag and only added poor heat resistance compared with the sample of comparative example 8 of Zr and each sample of embodiment 1～8.That is, confirm: the sample of comparative example 8 softens in the time heating 5 minutes for 400 DEG C, thereby makes Vickers' hardness be significantly less than 100Hv.
Confirm: the addition of Ag is less than poor heat resistance compared with the sample of comparative example 9 of 0.03 quality % and each sample of embodiment 1～8.That is, confirm: the sample of comparative example 9 softens in the time heating 5 minutes for 400 DEG C, thereby makes Vickers' hardness lower than 100Hv.
Confirm: the sample of comparative example 10 and each sample phase specific conductivity of embodiment 1～8 that the addition of Ag exceedes 0.1 quality % reduce, and can not maintain electric conductivity more than 95%IACS.In addition, confirm: by increasing the addition of Ag at high price, also producing manufacturing cost increases such problem.
Embodiment 9
In embodiment 9, while using high frequency melting furnace to make liquation, mix nitrogen and oxygen, under the atmosphere of oxygen partial pressure that is adjusted to regulation, make liquation, under this atmosphere, in liquation, add the Zr(0.004 quality % of specified amount) and Ag(0.050 quality %) and the liquation of making copper alloy.Other and above-described embodiment 1 similarly operate and make Cu alloy material.Set it as the sample of embodiment 9.
Embodiment 10 and comparative example 11～13
In embodiment 10 and comparative example 11～13, except having changed respectively oxygen partial pressure, similarly add the Zr of 0.004 quality % with above-described embodiment 9 and the Ag of 0.050 quality % makes Cu alloy material.Using them respectively as the sample of embodiment 10 and comparative example 11～13.
Comparative example 14
In comparative example 14, the copper alloy plate that the thickness having formed having carried out hot rolling processing is 8mm carries out cold-rolling treatment and makes the copper alloy plate that thickness is 1mm.The copper alloy plate that is 1mm to thickness carries out the thermal treatment (anneal) of 1 minute at 700 DEG C.Afterwards, under 80% degree of finish, carry out final cold-rolling treatment.Other and above-described embodiment 1 similarly operate and make the Cu alloy material that thickness is 0.2mm.Set it as the sample of comparative example 14.
To the embodiment 9～10 making as described above and each sample of comparative example 11～14, analyze the content of oxygen (O).In addition, to each sample of embodiment 9～10 and comparative example 11～14, measure respectively the Vickers' hardness before electric conductivity, heating, the Vickers' hardness 400 DEG C of heating after 5 minutes, the Vickers' hardness 450 DEG C of heating after 5 minutes, the stress mitigation rate 150 DEG C of heating after 1000 hours.To in these result sets, be shown in Table 3.
Table 3
Known as described in Table 3: if the content of the oxygen in Cu alloy material increases, the tendency that has thermotolerance to reduce.Confirmed by embodiment 9 and embodiment 10: if the content of the oxygen in Cu alloy material is below 0.001 quality %, 400 DEG C of heating, the Vickers' hardness after 5 minutes is more than 100Hv, has excellent thermotolerance.In addition, the stress mitigation rate that confirms the sample of embodiment 9 and embodiment 10 also can maintain below 30%.On the other hand, confirm: the sample that oxygen level exceedes the comparative example 11～13 of 0.001 quality % is less than 100Hv 400 DEG C of Vickers' hardnesses that heat after 5 minutes, and the rate of stress mitigation simultaneously exceedes 30%.By this results verification to: in order to maintain Vickers' hardness more than 100Hv 400 DEG C of heating after 5 minutes, the oxygen level in Cu alloy material must be adjusted into below 0.001 quality %.
In addition, confirmed by comparative example 14: if make the degree of finish of final cold-rolling treatment become large, even in the case of the Zr and Ag that have added specified amount, thermotolerance also reduces.
By above results verification to: use at least contain 0.003 quality % more than and the Zr below 0.01 quality % and the Ag more than 0.03 quality % and below 0.1 quality % and the content of oxygen is adjusted into the copper alloy below 0.001 quality % and the Cu alloy material of the present embodiment of obtaining, electric conductivity is more than 95%IACS, Vickers' hardness is more than 120Hv, to have high conductivity.Further, confirm: 400 DEG C of heating, the Vickers' hardness after 5 minutes is more than 100Hv to the Cu alloy material of such embodiments of the invention, and 150 DEG C of heating, the stress mitigation rate after 1000 hours is below 30% simultaneously, has excellent thermotolerance.Confirm: the Cu alloy material of embodiments of the invention has excellent thermotolerance in maintaining high conductivity.
Claims (7)
1. a Cu alloy material, is characterized in that, the Ag more than Zr more than at least containing 0.003 quality % and below 0.01 quality % and 0.03 quality % and below 0.1 quality %,
The content of oxygen is below 0.001 quality %,
Electric conductivity is more than 95%IACS,
Vickers' hardness is more than 120Hv.
2. Cu alloy material according to claim 1, is characterized in that, electric conductivity is more than 97%IACS.
3. Cu alloy material according to claim 1 and 2, is characterized in that, the Vickers' hardness 400 DEG C of heating after 5 minutes is more than 100Hv.
4. according to the Cu alloy material described in any one in claims 1 to 3, it is characterized in that, the Vickers' hardness 450 DEG C of heating after 5 minutes is more than 98Hv.
5. according to the Cu alloy material described in any one in claim 1 to 4, it is characterized in that, the stress mitigation rate 150 DEG C of heating after 1000 hours is below 30%.
6. a power distribution unit used for electric vehicle, is characterized in that, right to use requires the Cu alloy material described in any one in 1 to 5 and forms.
7. a power distribution unit for Hybrid Vehicle, is characterized in that, right to use requires the Cu alloy material described in any one in 1 to 5 and forms.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-003773 | 2013-01-11 | ||
| JP2013003773 | 2013-01-11 |
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| CN (1) | CN103924118B (en) |
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| JP6278812B2 (en) * | 2014-04-21 | 2018-02-14 | 株式会社Ｓｈカッパープロダクツ | Copper alloy material, distribution member for electric vehicle and distribution member for hybrid vehicle |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5077005A (en) * | 1989-03-06 | 1991-12-31 | Nippon Mining Co., Ltd. | High-conductivity copper alloys with excellent workability and heat resistance |
| CN101932741A (en) * | 2008-02-26 | 2010-12-29 | 三菱伸铜株式会社 | High strength and high conductivity copper rod and wire |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0644412B2 (en) * | 1989-04-10 | 1994-06-08 | 株式会社フジクラ | Copper composite wire for extra fine wire |
| JPH09118943A (en) * | 1995-10-23 | 1997-05-06 | Hitachi Cable Ltd | Oxygen-free copper alloy for vacuum equipment |
| JP4057436B2 (en) * | 2003-01-31 | 2008-03-05 | Ｄｏｗａホールディングス株式会社 | Copper base alloy and heat sink material using the copper base alloy |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5077005A (en) * | 1989-03-06 | 1991-12-31 | Nippon Mining Co., Ltd. | High-conductivity copper alloys with excellent workability and heat resistance |
| CN101932741A (en) * | 2008-02-26 | 2010-12-29 | 三菱伸铜株式会社 | High strength and high conductivity copper rod and wire |
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| JP2014148749A (en) | 2014-08-21 |
| JP6095562B2 (en) | 2017-03-15 |
| CN103924118B (en) | 2017-07-28 |
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