CN102639731B - Titanium-copper for electronic component - Google Patents
Titanium-copper for electronic component Download PDFInfo
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- CN102639731B CN102639731B CN201080053288.9A CN201080053288A CN102639731B CN 102639731 B CN102639731 B CN 102639731B CN 201080053288 A CN201080053288 A CN 201080053288A CN 102639731 B CN102639731 B CN 102639731B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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Abstract
Provided is titanium-copper which has excellent strength and bendability. The titanium-copper is a copper alloy for electronic components which contains 2.0-4.0 mass% Ti, the remainder comprising copper and incidental impurities. The intensity peak of X-ray diffraction from the {220} crystal plane in a rolled surface of the copper alloy has a half-value width [beta]{220} which satisfies the relationship 3.0=<[beta]{220}/[beta]0{220}<=6.0, wherein [beta]0{220} is the half-value width of the intensity peak of X-ray diffraction from the {220} crystal plane of a standard powder of pure copper. The copper alloy, in a structure examination of a section parallel to the rolling direction, has an average crystal-grain diameter of 30 [mu]m or smaller in terms of equivalent-circle diameter.
Description
Technical field
The present invention relates to the titanium copper and manufacture method thereof that are suitable as the electronic component-use components such as junctor.
Background technology
In recent years, with mobile terminal etc. for the miniaturization of the electronic machine of representative is in progress day by day, therefore, wherein used junctor requires that the tendency of thin space and slimming is remarkable.Miniature connector more requires that its pin widths is narrow, forms folding very little machining shape, and therefore, the component used requires to have high strength to obtain necessary elasticity, and have can the bendability of excellence of bending machining of resistance to harshness.In this respect, the strength ratio of the copper alloy (hereinafter referred to as " titanium copper ") containing titanium is higher, is the most excellent in copper alloy, therefore, all the time as there being the signal system terminal component of special requirement to use to intensity in stress relaxation characteristics.
Titanium copper is the copper alloy of age hardening type.Being formed the supersaturated solid solution of solute atoms Ti by solution treatment, implemented the thermal treatment of long period by this state with low temperature, then due to spinodal decomposition, make the cyclical movement of Ti concentration---modulated structure develops in parent phase, and intensity improves.Now produced problem is: intensity and bendability are opposing characteristic this point.That is, then bendability is impaired to improve intensity, on the contrary, if pay attention to bendability, cannot obtain desirable strength.Usually, improve cold rolling rate of compression, then the dislocation amount imported increases, and dislocation desity improves, and therefore increases the nucleation site contributing to separating out, can improve the intensity after ageing treatment, but if excessively improve rate of compression, bendability is deteriorated.Therefore, make intensity and bendability and be saved as the problem into research.
For this reason, people, from following viewpoint, propose and make the intensity of titanium copper and bendability and the technology of depositing: add the element such as Fe, Co, Ni, Si (patent documentation 1); Be limited in the concentration of the impurity element group of solid solution in parent phase, using them as second phase particles (Cu-Ti-X system particle), make it separate out, to improve the systematicness (patent documentation 2) of modulated structure with the distributional pattern of regulation; Specify (patent documentation 3) the trace additives of grain refining and the density of second phase particles effectively can be made; Make grain refining (patent documentation 4) etc.
When titanium copper, relative to parent phase α phase, there is the β phase (TiCu of consistence difference
3) and the good β ' phase (TiCu of consistence
4), β has detrimentally affect relative to bendability, and by β ' mutually evenly and disperse imperceptibly, contribute to intensity and bendability and deposit, therefore, people also proposed and make the mutually microdispersed titanium copper of β ' (patent documentation 5) while suppression β phase.
Also proposed following technology: be conceived to crystalline orientation, proposing by controlling crystalline orientation, making it meet I{420}/I
0{ 420}>1.0 and I{220}/I
0{ 220}≤3.0 improve intensity, bendability and proof stress slackness (patent documentation 6) thus.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2004-231985 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2004-176163 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2005-97638 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2006-265611 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2006-283142 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2008-308734 publication.
Summary of the invention
As mentioned above, in order to improve intensity and the bendability of titanium copper, have studied various method in the past, but still having room for improvement.Therefore, one of problem of the present invention is to improve from the characteristic that in the past different viewpoints attempts carrying out titanium copper, provides and has excellent intensity and the titanium copper of bendability.Another problem of the present invention is to provide the manufacture method of this titanium copper.
Titanium copper manufacture method is in the past be made up of the order of solution treatment → cold rolling → ageing treatment of the founding → homogenizing annealing → hot rolling of ingot → (annealing and cold rolling repeatedly carry out) → finally substantially.Titanium copper described in background technology is also manufacture by same order.
The present inventor is carrying out finding in the process studied for solving above-mentioned problem: the order of the cold rolling and ageing treatment of carrying out after by final solution treatment is opposite carries out, namely the order of ageing treatment → cold rolling is replaced with, and finally implement stress relieving with suitable condition, then bendability significantly improves.That is, by the titanium copper by order manufacture in the past compared with titanium copper of the present invention, then under same intensity, the bendability of titanium copper of the present invention is more excellent.The present inventor, in order to investigate its reason, is studied titanium copper tissue of the present invention, found that to have unique point in the form of dislocation desity and crystal grain.Specifically, when carrying out cold rolling with identical rate of compression, compared with when adopting the order of cold rolling → ageing treatment, when adopting the order of ageing treatment → cold rolling, the dislocation desity of gained titanium copper raises.In other words, can be reduced to obtain identical dislocation desity cold rolling time required rate of compression.Rate of compression is little, then when can suppress cold rolling, crystal grain be in the extension of rolling direction, and therefore bendability can improve.
Dislocation desity is difficult to direct mensuration.Its reason is distribution due to modulated structure or precipitation particles and causes the skewness of dislocation.When attempting indirect and evaluating, find that { half breadth at the X-ray diffraction intensity peak of 220} crystal face is relevant on calendering face.Half breadth is the width (β) of 1/2 intensity place diffracted intensity curve of peak intensity in diffracted intensity curve, with 2
θrepresent.Along with the rising of cold rolling shrinkage, half breadth increases together with dislocation desity.Therefore, in the present invention, with this half breadth for index, the state of indirect predetermined bits dislocation density.
Electronic component-use copper alloy according to one aspect of the present invention that above-mentioned cognition completes, this electronic component-use copper alloy contains 2.0-4.0 quality %Ti, rest part contains copper and inevitable impurity, wherein, from { half breadth β { the 220} and { the half breadth β at the X-ray diffraction intensity peak of 220} crystal face from fine copper standard powder at the X-ray diffraction intensity peak of 220} crystal face in calendering face
0220} meets following formula:
3.0≤β{220}/β
0{220}≤6.0，
And in the structure observation in the cross section parallel with rolling direction, average crystal particle diameter equivalent circle diameter represents, it is less than 30 μm.
In an embodiment of copper alloy of the present invention, in the structure observation in the cross section parallel with rolling direction, the average crystal particle diameter (L) in the direction parallel with rolling direction is 1-4 relative to the ratio (L/T) of the average crystal particle diameter (T) with the rectangular direction of rolling direction.
In another embodiment of copper alloy of the present invention, spring limit is 600-1000 MP a.
In the another embodiment of copper alloy of the present invention, spring limit is 300-600 MPa.
In the another embodiment of copper alloy of the present invention, one kind or two or more using what add up to 0-0.5 quality % to contain to be selected from as in Mn, Fe, Mg, Co, Ni, Cr, V, Nb, Mo, Zr, Si, B and P of element group.
Another aspect of the present invention is forged copper goods (Shen Copper product), these forged copper goods contain above-mentioned copper alloy.
Another aspect of the present invention is electronic unit, and this electronic unit possesses above-mentioned copper alloy.
Another aspect of the present invention is junctor, and this connection device is for above-mentioned copper alloy.
Another aspect of the present invention is the manufacture method of electronic component-use copper alloy, wherein, to Cu alloy material be heated at 730-880 DEG C the solid solution limit of Ti identical with addition time temperature more than carry out solution treatment, described Cu alloy material contains 2.0-4.0 quality %Ti, one kind or two or more using what add up to 0-0.5 quality % to contain to be selected from arbitrarily as in Mn, Fe, Mg, Co, Ni, Cr, V, Nb, Mo, Zr, Si, B and P of element group, and rest part contains copper and inevitable impurity;
After solution treatment, at material temperature 400-500 DEG C, carry out the ageing treatment heating 0.1-20 hour;
After ageing treatment, carrying out rate of compression is the finally cold rolling of 0-40%.
Comprise in an embodiment of the manufacture method of copper alloy of the present invention: after finally cold rolling, carry out stress relieving, this stress relieving is with material temperature more than 100 DEG C but lower than 350 DEG C of heating more than 0.001 hour less than 40 hours; With material temperature more than 350 DEG C but lower than 550 DEG C of heating more than 0.0001 hour less than 20 hours; Or with material temperature more than 550 DEG C less than 700 DEG C heating more than 0.0001 hour less than 0.003 hour.
Comprise in the another embodiment of the manufacture method of copper alloy of the present invention: after finally cold rolling, carry out stress relieving, this stress relieving is with material temperature more than 200 DEG C but lower than 400 DEG C of heating 0.001-20 hour.
According to the present invention, the titanium copper of intensity and excellent in bending workability can be obtained.
invention embodiment
< titanium content >
The strengthening mechanism that the formation that titanium then fully cannot obtain titanium copper modulated structure originally lower than 2.0 quality % brings, therefore cannot obtain enough intensity, on the contrary, more than 4.0 quality %, then easily separates out thick TiCu
3, intensity and bendability have the tendency that is deteriorated.Therefore, the Ti content in copper alloy of the present invention is 2.0-4.0 quality %, preferred 2.7-3.5 quality %.As mentioned above, by making the content of Ti suitable, intensity and the bendability of applicable electronic component-use can be realized simultaneously.
< element >
In titanium copper, add the element of regulation, even if then the high-temperature of abundant solid solution can carry out solution treatment with Ti, crystal grain is easily refinement also, has the effect that intensity is improved.In addition, the element of regulation promotes the formation of modulated structure.And then also there is the effect suppressing further Ti-Cu system stable phase sharply coarsening.Therefore titanium copper age hardening performance originally can be obtained.
In titanium copper, that above-mentioned effect is the highest is Fe.Mn, Mg, Co, Ni, Si, Cr, V, Nb, Mo, Zr, B and P also can expect the effect consistent with Fe, add separately and also show effect, also compound can add two or more.
Also can show above-mentioned effect although add up to containing these elements of more than 0.05 quality %, add up to more than 0.5 quality %, then the balance of intensity and bendability has the tendency that is deteriorated.Therefore, can be one kind or two or more using what add up to 0-0.5 quality % to contain to be selected from as in Mn, Fe, Mg, Co, Ni, Cr, V, Nb, Mo, Zr, Si, B and P of element group, preferably add up to containing 0.05-0.5 quality %.
< crystal particle diameter >
In order to improve intensity and the bendability of titanium copper, little crystal grain is suitable.Therefore, preferred average crystal particle diameter is less than 30 μm, more preferably less than 20 μm, further preferably less than 10 μm.Lower limit is not particularly limited, but due to crystal particle diameter distinguish become difficulty, therefore using such situation as being less than 1 μm (<1 μm), particle diameter little is like this also contained in scope of the present invention.But, if become extremely little, then stress relaxation characteristics reduces, therefore when needs stress relaxation characteristics, and preferably more than 1 μm.In the present invention, average crystal particle diameter is represented by following: passing through under opticmicroscope or electron microscope observation, the equivalent circle diameter in the structure observation in the cross section parallel with rolling direction.
Usually, crystal grain presents the elliptical shape extended along rolling direction according to finally cold rolling rate of compression, in order to improve bendability, preferably as far as possible close to positive round, makes the shape of crystal grain not have anisotropy.In the present invention, due to cold rolling rate of compression can be reduced, therefore can obtain and extend few crystal grain on rolling direction.But, in order to make the shape of crystal grain too reduce finally cold rolling rate of compression close to positive round, then undercapacity can be made.Therefore, in an embodiment of titanium copper of the present invention, by in the structure observation in the cross section parallel with rolling direction of electron microscope, with the average crystal particle diameter (L) of rolling direction parallel direction relative to the ratio (L/T) of the average crystal particle diameter (T) with the rectangular direction of rolling direction (hereinafter referred to as " crystal grain long-width ratio ".) be 1-4, preferred 1.5-3.5, more preferably 2-3.
< half breadth >
In the present invention, adopt calendering face { half breadth at the X-ray diffraction intensity peak of 220} crystal face is as the index of dislocation desity.This for the foregoing reasons.In titanium copper of the present invention, from { half breadth β { the 220} and { the half breadth β at the X-ray diffraction intensity peak of 220} crystal face from fine copper standard powder at the X-ray diffraction intensity peak of 220} crystal face in calendering face
0220} meets following formula:
3.0≤β{220}/β
0{220}≤6.0
β { 220} and β
0{ 220} measures under same measured condition.Fine copper standard powder is defined as the copper powder of the purity 99.5% of 325 orders (JIS Z8801).
β { 220}/β
0{ 220} reduces along with the reduction of dislocation desity, on the contrary, also raises along with the rising of dislocation desity.β { 220}/β
0{ 220} reduces, then bendability improves but intensity reduction.On the contrary, β { 220}/β
0{ 220} increases, then intensity improves but bendability reduction.In order to realize intensity and bendability and deposit, must be 3.0≤β { 220}/β
0{ 220}≤6.0, preferably 3.5≤β { 220}/β
0{ 220}≤5.0.In the manufacture method of carrying out according to the order of cold rolling → ageing treatment after final solution treatment as in the past, in order to make β { 220}/β
0220} is about 3.0, and must carry out rate of compression close to 50% cold rolling, but in manufacture method of the present invention, can to realize with rate of compression about 10%.Therefore, dislocation desity (intensity) can be improved, reduce crystal grain long-width ratio simultaneously, that is, do not damage bendability.
< spring limit >
In copper alloy of the present invention, can as described later, carry out regulating spring elastic limit according to whether implementing stress relieving in final operation.Therefore, required spring limit can be reached while the condition keeping above-mentioned half breadth or crystal grain.Such as in an embodiment of copper alloy of the present invention, the spring limit of 300-1000 MPa can be had, in the embodiment with high spring elastic limit, can be 600-1000 MPa, preferred 800-1000 MPa, in the embodiment with low spring limit, can be 300-600 MPa, be preferably 400-600 MPa.
< purposes >
Copper alloy of the present invention can provide as various forged copper goods such as plate, bar, pipe, rod and line.Titanium copper of the present invention is unrestricted, can be suitable as the electronic part materials such as switch, junctor, socket, terminal, rly. and use.
< manufacture method >
Titanium copper of the present invention can especially by implementing suitable thermal treatment and cold rollingly manufacturing in final solution treatment and operation afterwards.According to every procedure, applicable Production Example is described successively below.
1) manufacture of ingot
Substantially be carry out in a vacuum or in inert gas atmosphere by the manufacture melted and cast the ingot carried out.In melting, there is the melting residue of Addition ofelements, then cannot effectively act on the raising of intensity.Therefore, in order to eliminate melting residue, dystectic element such as Fe or Cr must fully stir after the addition, and keeps certain hour.And Ti ratio is easier to be dissolved in Cu, therefore can add after element is dissolved.Therefore, it is desirable to manufacture ingot as follows: in Cu, add be selected from Mn, Fe, Mg, Co, Ni, Cr, V, Nb, Mo, Zr, Si, B and P one kind or two or more, make it contain to add up to 0-0.5 quality %, then add Ti, make it contain with 2.0-4.0 quality %.
2) homogenizing annealing and hot rolling
Due to the solidifying segregation that produces when ingot manufactures or crystallisate thick, it is therefore desirable that make it be solid-solution in parent phase by homogenizing annealing thus make it reduce as far as possible, and eliminate as far as possible.This is effective for preventing bending crack.
Specifically, preferably carry out the homogenizing annealing of 3-24 hour at ingot manufacturing process post-heating to 900-970 DEG C, then implement hot rolling.For preventing liquid metal fragility, before preferred hot rolling and be less than 960 DEG C in hot rolling, and the passage (pass) being 90% by original thickness to reduced overall rate is more than 900 DEG C.Effectively reducing the segregation of Ti to cause suitable recrystallize in each passage, the draught of each passage can be implemented with 10-20 mm.
3) the 1st solution treatment
Afterwards, preferably cold rolling and annealing are suitably repeatedly carried out, then carry out solution treatment, here, the reason of carrying out solid solution is in advance the burden in order to alleviate final solution treatment.That is, final solution treatment is not used to the thermal treatment making Solid Solution of Second Phase Particles, but due to solid solution, as long as keep this state only to cause recrystallize simultaneously, therefore, can complete with slight thermal treatment.Specifically, the first solution treatment can make Heating temperature be 850-900 DEG C, carries out 2-10 minute.Preferably heat-up rate now and speed of cooling as quickly as possible, do not make second phase particles separate out at this yet.Also the first solution treatment can not be carried out.
4) calendering in the middle of
In the middle of before final solution treatment in calendering, more improve rate of compression and then more the recrystallize particle in final solution treatment can be controlled as even and fine.Therefore, the rate of compression of middle calendering is preferably 70-99%.Rate of compression is with { (thickness before (thickness after the thickness-calendering before calendering)/calendering) × 100%} defines.
5) final solution treatment
In final solution treatment, it is desirable to make the complete solid solution of precipitate, if but be heated to high temperature to eliminate completely, then crystal grain is easily thick, therefore Heating temperature be second phase particles composition solid solution limit near temperature (addition of Ti is when the scope of 2.0-4.0 quality %, temperature when the solid solution limit of Ti is equal with addition is about 730-840 DEG C, such as, when the addition of Ti is 3.0 quality %, is about 800 DEG C).If quickly heat up to this temperature and make speed of cooling also fast, then can suppress the generation of thick second phase particles.Therefore, typical mode be heat most 730-880 DEG C such make more than the temperature that the solid solution limit of Ti is identical with addition, more typically the temperature that make temperature height 0-20 DEG C that the solid solution limit of Ti with addition identical more such than 730-880 DEG C is heated to, the temperature of preferred high 0-10 DEG C.
In addition, the heat-up time of final solution treatment is shorter, then more can suppress the alligatoring of crystal grain.Heat-up time can be such as 30-90 second, is typically 30-60 second.In this moment, even if produce second phase particles, as long as fine and disperse equably, then to intensity and bendability almost harmless.But thick particle has the tendency of further growth in final ageing treatment, therefore, in this moment, though generate second phase particles also must try one's best less, as far as possible little.
6) ageing treatment
Ageing treatment is carried out after final solution treatment.Normally carried out cold rolling in the past after final solution treatment, but in order to obtain titanium copper of the present invention, importantly not carrying out cold rolling after final solution treatment, but carrying out ageing treatment immediately.Its reason is, and carries out compared with cold rolling situation before ageing treatment, even also can improve dislocation desity under same rate of compression.The present invention is not intended to be subject to theoretical restriction, but can think that this is relevant with the generation of shear zone with the crystallinity in crystal grain.Usually roll, then import dislocation, therefore crystal strain, half breadth increases.The little then crystallinity of half breadth is high, and half breadth greatly then crystallinity is low.Under the state that crystallinity is high, carry out ageing treatment to go forward side by side line bend processing, then shear zone easily develops, and easily forms the reason of bending crack.When carrying out timeliness after solid solution, evenly carry out evolution reaction in crystal grain, modulated structure or fine second phase particles easily evenly develop.Controlled as carrying out after such tissue cold rolling by timeliness, compared with when not carrying out timeliness, crystal more easily strains, and shear zone is more difficult to development.But degree of finish improves, and dislocation desity excessively increases, and damages bendability.Therefore, even low degree of finish also can suppress the development of shear zone, obtain high strength simultaneously.Ageing treatment carries out ageing treatment after solution treatment, therefore, reduces, so can carry out under than common aging condition slightly high temperature as the strain of separating out motivating force.Specifically, preferably at material temperature 400-500 DEG C, heat 0.1-20 hour, more preferably at material temperature 400-480 DEG C, heat 1-16 hour.
7) final cold rolling
Carry out final cold rolling after above-mentioned ageing treatment.The intensity of titanium copper can be improved by final cold rolling processing.Also can not implement this cold rolling, but when to obtain for the purpose of high strength, rate of compression is more than 5%, preferably more than 10%, more preferably more than 15%.But, the long-width ratio of the too high then crystal grain of rate of compression increases excessive, and the raising effect of bendability reduces, and therefore, rate of compression is less than 40%, and preferably less than 30%, more preferably less than 25%.
8) stress relieving
According to the structure of electronic unit, require different shape processing.Usually, work hardening is carried out at the position of implementing the viscous deformation such as bending machining or grooving processing, and the strength of materials more improves.Guarantee that the structure crimped is difficult to viscous deformation by such bending machining portion, therefore do not need high spring limit.Therefore stress relieving can not be carried out in such use.
On the other hand, by the shape after punching press add do not guarantee to crimp by the position of viscous deformation man-hour structure (such as by the contact portion of terminal to the structure of straight line portion (arm) distance in bending machining portion, or as the structure not implementing grooving processing or bending machining of forked terminal, the structure that stress in bending puts on arm), the resistance for sag must be had, therefore, high spring limit is important.
Therefore, in the purposes that particularly spring limit is important wherein, final cold rolling after carry out stress relieving.Particularly when final cold rolling rate of compression is more than 3%, in the purposes that spring limit is important, preferably carry out stress relieving wherein.In addition, when final cold rolling rate of compression is more than 10%, in the purposes that spring limit is important, particularly preferably stress relieving is carried out wherein.The condition of stress relieving can be usual condition, but by the dislocation uneven distribution of cold rolling importing.By carrying out stress relieving, making dislocation rearrangement, the further raising of intensity can be realized thus.But, if excessively carry out stress relieving, then dislocation disappears, and intensity reduces, therefore not preferred.Therefore, can be such as the heating carried out with material temperature more than 100 DEG C but lower than 350 DEG C more than 0.001 hour less than 40 hours, the heating of more than 0.0001 hour less than 20 hours is carried out with material temperature more than 350 DEG C but lower than 550 DEG C, or the heating of more than 0.0001 hour less than 0.003 hour is carried out with material temperature more than 550 DEG C less than 700 DEG C, preferably to carry out lower than under 400 DEG C of heating condition of 0.001-20 hour material temperature more than 200 DEG C, more preferably to carry out lower than under 550 DEG C of heating condition of 0.001-0.5 hour material temperature more than 350 DEG C, more preferably if low temperature is then with long-time (such as with material temperature 200-300 DEG C of heating 10-20 hour), if high temperature then carries out with the condition of short period of time (such as with less than material temperature 550-700 DEG C heating 0.001-0.003 hour).
Those skilled in the art should understand, and suitably can carry out the operation such as grinding, grinding, sandblasting pickling of the oxide skin for removing surface in the interval of above-mentioned each operation.
embodiment
Together with comparative example, embodiments of the invention are shown below, these embodiments provide to understand the present invention and advantage thereof better, is not intended to limit invention.
When manufacturing the copper alloy of example of the present invention, add active metal Ti as the 2nd composition, therefore, found middle employing vacuum melting stove.In addition, being mixed into of the impurity element beyond element given to this invention may cause the side effect outside anticipation to occur, and for preventing trouble before it happens, raw material strictly need choose the higher materials'use of purity.
First, form by table 1 Suo Shi, in Cu, add Mn, Fe, Mg, Co, Ni, Cr, V, Nb, Mo, Zr, Si, B and P respectively, then add the Ti of composition shown in this table respectively.Take into full account the hold-time after interpolation, make Addition ofelements there is no melting residue, then they are injected mold under an ar atmosphere, manufacture the ingot of about 2 kg respectively.
[table 1]
Table 1. Addition ofelements (quality %)
。
At 950 DEG C, 3 hours are heated to above-mentioned ingot, carry out homogenizing annealing, then at 900-950 DEG C, carry out hot rolling, obtain the hot-rolled sheet of thickness of slab 10 mm.By surfacing deoxygenated skin, then carry out cold rolling, make thickness of slab (2.0 mm) base bar, carry out the 1st solution treatment with base article.The condition of the 1st solution treatment heats 10 minutes at 850 DEG C.The 1st solution treatment is not carried out in a part of embodiment.Then, centre cold rolling in, cold rolling regulate in the middle of thickness of slab, make final thickness of slab be 0.10 mm, be then inserted into and in the annealing furnace of rapid heating, final solution treatment can be carried out, then water-cooled.Heating condition is now: temperature when material temperature is identical with addition with the solid solution limit of Ti (during Ti concentration 3.0 quality %, is about 800 DEG C; During Ti concentration 2.0 quality %, be about 730 DEG C; During Ti concentration 4.0 quality %, be about 840 DEG C) consistent, and keep 1 minute respectively according to the heating condition shown in table 2.Then, ageing treatment is carried out according to condition described in table 2 in an ar atmosphere.By carrying out cold rolling according to condition described in table 2 after pickling deoxygenated skin, finally annealing according to heating condition each described in table 2, making the test film of example and comparative example.According to the difference of test film, ageing treatment immediately after solution treatment can be omitted.
[table 2]
。
For each test film of gained, carry out evaluating characteristics according to following condition.Result is as shown in table 3.
< intensity >
Use press, make JIS13B test film, make draw direction parallel with rolling direction.Carry out the tension test of this test film according to JIS-Z2241, measure 0.2% yield strength (YS) of calendering parallel direction.
< bendability >
A:W bends
According to JIS H3130, implement the W pliability test of Badway (bending axis and rolling direction are same direction) with the mould that bending radius is 2 times of thicknesss of slab, when there is not crackle, be set to zero, be set to when there is crackle ×.
B:180 ° bends
Test film is pressed on the angle of the block of the fillet radius (R) with regulation, carry out 90 ° to bend, clamp the plate (fillet radius R) of 2 times of thickness (2R) of this fillet radius in the inner side in 90 ° of bending machining portions, the end face along plate bends 180 °.Minimum bending radius (R) when outside curved surface after 180 ° of bending machining not being produced crack divided by thickness of slab (t), using the index of income value (R/t) as bendability.
Fillet radius changes 0.01 mm at every turn.
< specific conductivity >
According to JIS H0505, measure specific conductivity (EC:%IACS) by four-terminal method.
< average crystal particle diameter >
The mensuration of average crystal particle diameter is cut off in the cross section parallel with rolling direction with FIB, and cross section is exposed, and then SIM observes cross section, and the number of dies of tally's area, obtains the leveled circular equivalent diameter of crystal grain.Specifically, make the frame of 100 μm × 100 μm, counting is present in the number of the crystal grain in this frame.1/2 is all counted as the crystal grain across in-out-snap.By the area 10000 μm of frame
2divided by this total, obtain the mean value of the area of every 1 crystal grain.The positive circular diameter with this area is equivalent circle diameter, therefore it can be used as average crystal particle diameter.
< crystal particle diameter long-width ratio >
By electrolytic polishing, the tissue in the cross section parallel with rolling direction is exposed, taken the field of view of 100 μm × 100 μm afterwards by electron microscope (Philips company manufactures, XL30 SFEG).According to JIS H0501, obtain the average crystal particle diameter in the rectangular direction with rolling direction and the average crystal particle diameter with rolling direction parallel direction by the process of chopping, calculate long-width ratio.
< half breadth >
To each test film, the X-ray diffraction device of the model rint Ultima2000 using motor society of science to manufacture, obtains the diffracted intensity curve in calendering face by following condition determination, measures { half breadth β { the 220} at the X-ray diffraction intensity peak of 220} crystal face.With same condition determination, half breadth β is obtained to fine copper powder standard test specimen
0{ 220}.In copper powder standard test specimen, { 2 of the peak in 220} face
θoccur near 74 °.
Target: Cu pipe ball
Tube voltage: 40 kV
Tube current: 40 mA
Sweep velocity: 5 °/minute
Sampling width: 0.02 °
Measurement range (2
θ): 60 °-80 °.
< spring limit (Kb) >
Spring limit (Kb) implements repeatedly flexure test according to JIS H3130 (alloy numbering C1990), measures surperficial maximum stress by the moment of flexure of residual permanent strain.
[table 3]
。
< investigates >
Intensity and the bending machining sexual balance of known example No.1-25 improve well.Example 13-26 is variation manufacturing process being applied to change.In example 13, the solid solution temperature of the 2nd time is set higher, obtains the average crystal particle diameter of the upper limit.Rate of compression finally cold rolling in example 14 is low, and therefore, β is the lower limit of required scope, and long-width ratio also reduces, but also in the scope of regulation of the present invention, therefore, intensity and bending machining sexual balance improve well.Example 15, compared with example No.4, is result aging temperature being set as lower limit.Example 16, compared with example No.4, is result aging temperature being set as the upper limit.Example 17 and 18 is the examples of the operation stress relieving eliminating example No.2 and example No.4 respectively, eliminates stress relieving even if known, and β value is still in specialized range of the present invention, and intensity and bending machining sexual balance improve well.Relative to example 17 and 18, example 19,20 and 21 has carried out stress relieving, and intensity and Kb value improve thus.Example 22-25 is the example of omission the 1st solution treatment, and then No.24 and 25 is the examples not carrying out stress relieving, omit the solution treatment of the 1st time even if known and do not carry out stress relieving, β value is still in specialized range of the present invention, and intensity and bending machining sexual balance improve well.Example 26 is the examples to carry out stress relieving between low-temperature short-time.
On the other hand, in comparative example No.1-3, after solution treatment, do not carry out ageing treatment but carry out cold rolling, therefore half breadth is little, and the equilibrium ratio example of intensity and bendability is poor.In addition, in comparative example No.4-5, after solution treatment, carried out ageing treatment, but in comparative example No.4, cold rolling rate of compression improves, and half breadth excessively increases, and therefore the equilibrium ratio example of intensity and bendability is poor.In comparative example No.5, the Heating temperature of solution treatment is too high, and therefore crystal particle diameter increases.Final cold rolling rate of compression is high, although therefore obtain higher intensity, bendability is poor.In comparative example No.6,7,9 and 10, solid solubility temperature is too high, and therefore crystal particle diameter exceedes the upper limit, and bendability is deteriorated.In addition, in comparative example 7 and 8, do not carry out ageing treatment after solution treatment but carry out cold rolling, therefore half breadth is little, the balanced differences of intensity and bendability.Comparative example No.11 at high temperature carries out stress relieving, therefore initial recrystallization, causes dislocation desity to reduce and β reduction, and starts solid solution again, therefore causes intensity and specific conductivity to reduce.
Claims (11)
1. electronic component-use copper alloy, this copper alloy contains 2.0-4.0 quality %Ti, rest part contains copper and inevitable impurity, wherein, from { half breadth β { the 220} and { the half breadth β at the X-ray diffraction intensity peak of 220} crystal face from fine copper standard powder at the X-ray diffraction intensity peak of 220} crystal face in calendering face
0220} meets following formula:
3.0≤β{220}/β
0{220}≤6.0，
Further, in the structure observation in the cross section parallel with rolling direction, average crystal particle diameter equivalent circle diameter represents, is less than 30 μm.
2. the copper alloy of claim 1, wherein, in the structure observation in the cross section parallel with rolling direction, the average crystal particle diameter (L) in the direction parallel with rolling direction is 1-4 relative to the ratio (L/T) of the average crystal particle diameter (T) with the rectangular direction of rolling direction.
3. the copper alloy of claim 1 or 2, wherein, spring limit is 600-1000 MP a.
4. the copper alloy of claim 1 or 2, wherein, spring limit is 300-600 MPa.
5. the copper alloy any one of claim 1-4, wherein, one kind or two or more using what add up to 0-0.5 quality % to contain to be selected from as in Mn, Fe, Mg, Co, Ni, Cr, V, Nb, Mo, Zr, Si, B and P of element group.
6. forged copper goods, it contains the copper alloy any one of claim 1-5.
7. electronic unit, it possesses the copper alloy any one of claim 1-5.
8. junctor, it possesses the copper alloy any one of claim 1-5.
9. the manufacture method of electronic component-use copper alloy, wherein, Cu alloy material is carried out to the homogenizing annealing of 3-24 hour at 900-970 DEG C, then less than 960 DEG C are carried out, and the passage being 90% by original thickness to reduced overall rate is the hot rolling of more than 900 DEG C, then in the solution treatment of 730-880 DEG C of temperature above 30-90 second of carrying out temperature height 0-20 DEG C when being heated to more identical with addition than the solid solution limit of Ti, described Cu alloy material contains 2.0-4.0 quality %Ti, the Mn be selected from arbitrarily as element group is contained to add up to 0-0.5 quality %, Fe, Mg, Co, Ni, Cr, V, Nb, Mo, Zr, Si, one kind or two or more in B and P, and rest part contains copper and inevitable impurity, after solution treatment, at material temperature 400-500 DEG C, carry out the ageing treatment heating 0.1-20 hour, after ageing treatment, carry out rate of compression is the finally cold rolling of 0-40%.
10. the manufacture method of the electronic component-use copper alloy of claim 9, its be included in finally cold rolling after carry out stress relieving, this stress relieving is with material temperature more than 100 DEG C but lower than 350 DEG C of heating more than 0.001 hour less than 40 hours; With material temperature more than 350 DEG C but lower than 550 DEG C of heating more than 0.0001 hour less than 20 hours; Or with material temperature more than 550 DEG C less than 700 DEG C heating more than 0.0001 hour less than 0.003 hour.
The manufacture method of the electronic component-use copper alloy of 11. claims 9, its be included in finally cold rolling after carry out stress relieving, this stress relieving is with material temperature more than 200 DEG C but lower than 400 DEG C of heating 0.001-20 hour.
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| JP2010145045A JP4889801B2 (en) | 2009-11-25 | 2010-06-25 | Manufacturing method of titanium copper for electronic parts |
| PCT/JP2010/069369 WO2011065188A1 (en) | 2009-11-25 | 2010-10-29 | Titanium-copper for electronic component |
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| CN102686755A (en) * | 2009-11-25 | 2012-09-19 | Jx日矿日石金属株式会社 | Titanium-copper for electronic component |
| JP4961049B2 (en) * | 2009-11-25 | 2012-06-27 | Ｊｘ日鉱日石金属株式会社 | Titanium copper for electronic parts |
| JP5319590B2 (en) * | 2010-03-30 | 2013-10-16 | Ｊｘ日鉱日石金属株式会社 | Copper alloy, copper alloy manufacturing method and electronic component manufacturing method |
| JP5393629B2 (en) * | 2010-09-30 | 2014-01-22 | Ｊｘ日鉱日石金属株式会社 | Titanium copper and copper products, electronic parts and connectors using the same |
| JP5542898B2 (en) * | 2012-10-24 | 2014-07-09 | Ｊｘ日鉱日石金属株式会社 | Camera module and titanium copper foil |
| JP6192917B2 (en) * | 2012-10-25 | 2017-09-06 | Ｊｘ金属株式会社 | High strength titanium copper |
| JP6192916B2 (en) * | 2012-10-25 | 2017-09-06 | Ｊｘ金属株式会社 | High strength titanium copper |
| JP6125410B2 (en) * | 2013-11-15 | 2017-05-10 | Ｊｘ金属株式会社 | Titanium copper for electronic parts |
| JP6125409B2 (en) * | 2013-11-15 | 2017-05-10 | Ｊｘ金属株式会社 | Titanium copper for electronic parts |
| EP3088543A4 (en) | 2013-12-27 | 2017-08-16 | Furukawa Electric Co., Ltd. | Copper alloy sheet material, connector, and production method for copper alloy sheet material |
| EP3088542A4 (en) | 2013-12-27 | 2017-08-16 | Furukawa Electric Co., Ltd. | Copper alloy sheet material, connector, and production method for copper alloy sheet material |
| JP6073268B2 (en) | 2014-08-29 | 2017-02-01 | Ｊｘ金属株式会社 | High strength titanium copper foil and method for producing the same |
| JP6080820B2 (en) | 2014-08-29 | 2017-02-15 | Ｊｘ金属株式会社 | High strength titanium copper foil and method for producing the same |
| JP6228941B2 (en) * | 2015-01-09 | 2017-11-08 | Ｊｘ金属株式会社 | Titanium copper with plating layer |
| KR101875807B1 (en) * | 2018-03-14 | 2018-07-06 | 주식회사 풍산 | Method for manufacturing a copper alloy material for automobiles and electric/electronic parts excellent in high strength and bending workability |
| JP6629400B1 (en) * | 2018-08-30 | 2020-01-15 | Ｊｘ金属株式会社 | Titanium copper plate before aging treatment, pressed product and method for producing pressed product |
| CN109355526B (en) * | 2018-11-06 | 2020-07-17 | 有研工程技术研究院有限公司 | High-elasticity copper-titanium alloy and tissue regulation method thereof |
| JP7038879B1 (en) * | 2021-07-20 | 2022-03-18 | Ｄｏｗａメタルテック株式会社 | Cu-Ti copper alloy plate material, its manufacturing method, and current-carrying parts |
| CN113802027B (en) * | 2021-09-18 | 2022-07-15 | 宁波博威合金板带有限公司 | Titanium bronze and preparation method thereof |
| CN114150123B (en) * | 2021-11-24 | 2024-03-12 | 中铝科学技术研究院有限公司 | Method for effectively improving alloy strength and conductivity |
| CN114836649B (en) * | 2022-03-29 | 2023-10-13 | 兰州兰石集团有限公司铸锻分公司 | Large titanium copper forging and manufacturing method thereof |
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