CN105671358B - Copper alloy plate, copper alloy part and connector - Google Patents
Copper alloy plate, copper alloy part and connector Download PDFInfo
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- CN105671358B CN105671358B CN201610130170.0A CN201610130170A CN105671358B CN 105671358 B CN105671358 B CN 105671358B CN 201610130170 A CN201610130170 A CN 201610130170A CN 105671358 B CN105671358 B CN 105671358B
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- copper alloy
- alloy plate
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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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- 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
Abstract
The present invention provides a kind of copper alloy plate, copper alloy part and connector, the copper alloy plate excellent in bending workability, has excellent intensity, is suitable for lead frame, connector, terminal material of electric/electronic device etc.；And the connector of automobile mounted use etc. or terminal material, relay, switch etc.；The copper alloy plate contains the mass % of 1.0 mass %~5.0 Ti, and remainder is made up of copper and inevitable impurity；In the crystal orientation analysis that the EBSD in sheet metal thickness direction is determined, Cube orientations { 001 }<1 0 0>Area occupation ratio be 5%~50%.The copper alloy part and connector of the present invention is made up of the copper alloy plate.
Description
The application is the division Shen for PCT International Application Serial No. PCTs/JP2011/069467 that the applying date is on 08 29th, 2011
Please, original application is application for a patent for invention, into the Application No. 201180040769.0 of thenational phase, entitled " copper alloy plate
Material and its manufacture method ".
Technical field
The present invention relates to copper alloy plate and its manufacture method, and specifically the present invention relates to one kind to be applied to such as lead
The on-vehicle parts such as framework, connector, terminal material, relay, switch, socket, engine with or electric/electronic device portion
The copper alloy plate and its manufacture method of part.
Background technology
For be used in on-vehicle parts with or the lead frame of electric/electronic device, connector, terminal material, relay
Characteristic project required by the copper alloy plate of the purposes such as device, switch, socket has conductance, yield strength (yield stress), drawn
Stretch intensity, bendability, stress relaxation-resistant characteristic.In recent years, with the miniaturization, lightweight, Gao Xing of electric/electronic device
The high temperature of energyization, high-density installation and use environment, the requirement for these characteristics also improve therewith.
In the past, under normal conditions, in addition to ferrous material, the copper alloy of phosphor bronze, red metal, brass etc. is widely used
Based material is as electric/electronic device material.These copper alloys are the solution strengthening by Sn or Zn with being based on calendering or wire drawing
Intensity is improved Deng the combination of the processing hardening of cold working.In method, conductance is simultaneously insufficient, and higher due to applying
Cold working rate obtain high intensity, therefore bendability or stress relaxation-resistant characteristic and insufficient.
As its intensifying method is substituted, the precipitation strength for separating out the second fine phase in the material there are.This strengthens
Method also has the advantages of can lifting conductance simultaneously, therefore be carried out in many alloy systems in addition to intensity improves.But
With the miniaturization of recent electronic equipment or automotive part, used copper alloy plate is changed into the copper conjunction to higher intensity
Golden based material implements bending machining with more minor radius, is strongly required a kind of copper alloy plate of excellent in bending workability.Conventional
Cu-Ti systems in, calendering working modulus is improved to obtain high intensity and is hardened with obtaining big processing, but as it was earlier mentioned, this
Kind method can deteriorate bendability, can not take into account high intensity and good bendability simultaneously.
Requirement for the raising bendability, it has been suggested that several by controlling crystal orientation the scheme that solves.Example
Such as it is disclosed below for the copper alloy of Cu-Ni-Si systems.In patent document 1, find in Cu-Ni-Si series copper alloys, tie
The situation of crystal orientation of the crystal size with meeting a certain condition from { 311 }, { 220 }, the X-ray diffraction intensity I in { 200 } face
Under, excellent in bending workability.In addition, in patent document 2, find in Cu-Ni-Si series copper alloys, from { 200 } and
{ 220 } in the case that the X-ray diffraction intensity in face meets the crystal orientation of a certain condition, excellent in bending workability.In addition, special
In sharp document 3, find in Cu-Ni-Si series copper alloys, by controlling Cube to be orientated { 100 }<001>Ratio can add bending
Work is excellent.
In addition, it is disclosed below for Cu-Ti series copper alloys.In patent document 4, (311) face is grown up, make I
(311)/I (111) >=0.5, so as to lift stampability.In patent document 5, it is proposed that a kind of copper alloy plate, it is logical
Cross and change the addition of the third element beyond Ti and Ti, with the temperature in each stage in the hot calender of two benches progress and calendering
Rate, the working modulus of cold calendaring, solutionizing treatment conditions, Precipitation condition, meet average crystal grain footpath and copper alloy so as to have
X-ray diffraction intensity I { 420 }/I of the plate face of sheet material0{420}>1.0 crystallization orientation, intensity height and otch
(notching) excellent in bending workability after.An Albatra metal is proposed in patent document 6, it is except changing the bar that homogenizes
Beyond part, the final passage temperature of hot calender, the average processing temperature of each passage of hot calender, also change consolidating with the progress of 2 stages
Treatment conditions are dissolved, degree of finish, the aging condition of cold calendaring that each solutionizing processing is carried out afterwards, so as to high intensity, excellent
Different bendability and high-dimensional stability.In patent document 7, it tries be orientated by obtaining based on { 200 } crystal face
The recrystallization set tissue of composition, so as to have intensity and bendability concurrently.
In addition, as one of characteristic project to being used in required by the copper alloy plate of electric/electronic device purposes,
Ask Young's modulus (longitudinal modulus of elasticity) low.In recent years, as the electronic units such as connector constantly minimize, the size of terminal
The tolerance of precision and punch process also more becomes strict.By reducing the Young's modulus of copper alloy plate, can reduce dimensional variations to
The influence that the contact of contact is brought, therefore may be such that design becomes easy.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2006-009137 publications
Patent document 2：Japanese Unexamined Patent Publication 2008-013836 publications
Patent document 3：Japanese Unexamined Patent Publication 2006-283059 publications
Patent document 4：Japanese Unexamined Patent Publication 2006-249565 publications
Patent document 5：Japanese Unexamined Patent Publication 2010-126777 publications
Patent document 6：Japanese Unexamined Patent Publication 2007-270267 publications
Patent document 7：Japanese Unexamined Patent Publication 2011-26635 publications
The content of the invention
However, in the invention described in patent document 1 and patent document 2, from certain surface obtained by X-ray diffraction
Crystal orientation the analysis distribution that only relates to there is the crystal orientation of a certain width in minimum a part of certain surface.In addition,
In the invention that patent document 3 is recorded, more than 50% is improved by the way that the Cube of Cu-Ni-Si alloy is orientated into area occupation ratio, so as to
Have intensity and bendability concurrently.Herein, the control of crystal orientation be by reduce solutionizingization heat treatment after calendering process
Rate is realized.In the invention that patent document 4 is recorded, by carrying out cold calendaring in the state of solute atoms is dissolved completely,
(311) face is grown up, and make I (311)/I (111) >=0.5, so as to lift stampability.Manufacturing process is by cold calendaring, again tied
Crystalline substance annealing and subsequent process carry out tropism control.In patent document 5, by make average crystal grain footpath for 5 μm~25 μm,
And control the set tissue using { 420 } crystal face as main orientation component, thus lift the bendability after otch.In manufacturer
In method, though there are the related record of hot calender condition, cold calendaring condition, solutionizing heat treatment condition, Precipitation condition, hot pressing
Prolonging was carried out in a manner of 2 stages, and intermediate annealing before being heat-treated without solutionizing and cold pressing immediately after
Solutionizing processing is carried out under conditions of prolonging.In patent document 6, it is used as Second Phase Particle by separating out third element group, from
And make to be formed at wavelength, the amplitude stability of the concentration wave (so-called deformation texture) of the titanium in parent phase.Further by this
The number density of Second Phase Particle is controlled, so as to have intensity and bendability, and the size essence of punch process concurrently
Degree is also improved.In a manufacturing method, the cold calendaring working modulus before final solutionizing is up to 70%~99%, also,
One and the final solutionizing carried out with two benches processing in, thermal process with it is given to this invention entirely different.In patent
In document 7, the average grain diameter of recrystallization grain is controlled with solutionizing heat treatment, is obtained using { 200 } crystal face as main orientation component
Recrystallization set tissue, thus has intensity and bendability concurrently.In process, the intermediate annealing after cold calendaring is at 450 DEG C
~600 DEG C are kept for 1 hour~20 hours, different greatly with the condition of the present invention.It is though in addition, strong by the diffraction for improving I { 200 }
Degree improves bendability, but on bending the reduction of gauffer, Young's modulus, bending coefficient are not recorded then.
On the other hand, it is right as electric/electronic device in recent years increasingly minimizes, high performance, high-density installation etc.
In the copper alloy plate of electric/electronic device, gradually require contemplated more curved than in the invention described in above-mentioned each patent document
The taller bendability of bent processability, and also require to reduce the bending gauffer of bending machining surface portion.
Cu-Ti is cast and needs to carry out in inert gas or in vacuum melting furnace due in order to prevent Ti oxidation, but
Even so, may also can there are the thick crystal and precipitate being made up of oxide in ingot bar, and when implementation more than 80%
When forcing work (cold calendaring), indexable (translocation position), strain occur around them, and in the recrystallization for making Cube orientation growth
Orientation rotation is hindered in solutionizing heat treatment.
In view of the above problems, problem of the invention is to provide a kind of copper alloy plate and its manufacture method, and the copper closes
The excellent in bending workability of golden plate material, there is excellent intensity, and be suitable for the lead frame of electric/electronic device, connection
Device, terminal material etc.；And the connector of automobile mounted use etc. or terminal material, relay, switch etc..
The means used to solve the problem
After the present inventor is studied the copper alloy plate for being suitable for electrical and electronic parts purposes, find in Cu-Ti systems
In copper alloy, in order that bendability, intensity, electric conductivity, stress relaxation-resistant characteristic are substantially improved, Cube orientation assembly ratios
It is related between bendability, after concentrating on studies, learn by specific copper alloy composition, controlling as spy
Fixed orientation set tissue, so as to significantly lift these desired characteristics.Also, with the crystal orientation and spy
Property copper alloy plate in, it was found that have can further be lifted intensity effectiveness addition element, in addition, also in this alloy system
In be found that with will not damage conductance and bendability and the addition element of the effectiveness of intensity can be lifted.And it was found that
By the way that with certain working procedure, and the manufacture method formed, the certain working procedure is to be used to realize crystal orientation as described above.This
Invention is completed based on these opinions.
That is, following means can be provided according to the present invention.
(1) a kind of copper alloy plate, its be containing 1.0 mass %~5.0 mass % Ti, remainder is substantially by copper
And the copper alloy plate that inevitably impurity is formed, the copper alloy plate are characterised by, in the crystal orientation of EBSD measure
In analysis, Cube orientations { 001 }<1 0 0>Area occupation ratio be 5%~50%；
(2) copper alloy plate as described in (1), it is characterised in that the copper alloy further adds up to and contains 0.005 matter
Measure the mass % of %~1.0 at least one in the group being made up of Sn, Zn, Ag, Mn, B, P, Mg, Cr, Zr, Si, Fe and Hf
Kind；
(3) copper alloy plate as described in (1) or (2), it is characterised in that 0.2% yield strength is more than 850MPa, curved
Bent processability is less than 1, and the bendability is small for that can carry out flawless and bending gauffer in 90 ° of W crooked tests
Value (r/t) obtained by the minimum bending radius (r, mm) divided by thickness of slab (t, mm) of bending machining；
(4) copper alloy plate as described in any one of (1)~(3), it is characterised in that represent to apply constant stress to sheet material
When it is displacement, using the Young's modulus that stretching test measurement obtains as 90GPa~120GPa, determine what is obtained with bending test
Bending coefficient is 80GPa~110GPa；
(5) a kind of manufacture method of copper alloy plate, it is the copper alloy plate described in any one of (1)~(4) described in manufacture
The method of material, it is characterised in that the alloying component by forming the copper alloy plate is formed formed copper alloy raw material according to
Sequence implements casting [process 1], the heat treatment that homogenizes [process 2], hot calender [process 3], water cooling [process 4], cold calendaring [process
6], intermediate annealing [process 7], cold calendaring [process 8] and middle solutionizing heat treatment [process 9]；
(6) manufacture method of the copper alloy plate as described in (5), it is characterised in that be heat-treated in the middle solutionizing
After [process 9], sequentially implement Precipitation heat treatment [process 10], cold sperm calendering [process 11] and quenched annealing [process
12]；
(7) one Albatra metal parts, it is made up of the copper alloy plate described in any one of above-mentioned (1)~(4)；And
(8) a kind of connector, it is made up of the copper alloy plate described in any one of above-mentioned (1)~(4).
The excellent in bending workability of the copper alloy plate of the present invention, shows excellent intensity, has and is particularly suitable for electricity
The lead frame of gas electronic equipment, connector, terminal material etc. and it is automobile mounted with etc. connector or terminal material, relay
The property of device, switch etc..In addition, manufacturing method according to the invention, can suitably manufacture above-mentioned copper alloy plate.
The copper alloy plate of the present invention has containing 1.0 mass %~5.0 mass % Ti, and remainder is by copper and can not
The composition that the impurity avoided is formed, in the crystal orientation analysis of EBSD measure, Cube orientations { 001 }<1 0 0>Area
Rate is 5%~50%, therefore each excellent of intensity, bendability, conductance, stress relaxation-resistant characteristic, using the teaching of the invention it is possible to provide
It is suitable for the copper alloy of automobile mounted use or the purposes of electric/electronic device.
The above-mentioned and further features and advantages of the present invention can be by appropriate referring to the drawings, by following records and more clear
Chu.
Brief description of the drawings
Fig. 1 is to represent from { 001 }<100>The deviation angle that Cube has been orientated is the schematic diagram of the example within 10 °.
Fig. 2 is the explanation figure of the test method of stress relaxation-resistant characteristic；Fig. 2 (a) represents the state before heat treatment, Fig. 2 (b)
Then represent the state after heat treatment.
Fig. 3 is based on JCBA T309:The explanation figure of the stress relaxation test method of 2001 (tentative).
Symbol description
1 assigns test film during primary stress
Test film after 2 elimination capacities
Test film during 3 non-loading stress
4 testing stands
11 test films (during elimination capacity)
12 test fixtures
13 reference planes
14 flexural loads bolts
15 test films (during flexural loads)
Embodiment
It is described in detail for the preferred embodiment of the copper alloy plate of the present invention.Herein, " Cu alloy material "
Refer to copper alloy raw material (forming before processing and with defined alloy) being processed as regulation shape (such as plate, bar, paper tinsel, rod, line
Deng) obtained from material.Wherein, so-called sheet material refers to specific thickness and dimensionally stable, in the surface direction with width
The material of degree, broadly comprising web.In the present invention, for the thickness of sheet material, there is no particular restriction, if but considering
Make the effect of the present invention more notable and be suitable for practical use, then preferably 0.01mm~1.0mm, more preferably 0.05mm~
0.5mm。
It should be noted that in the copper alloy plate of the present invention, to roll the assembly rate of the atomic plane of the prescribed direction of plate
And its characteristic is defined, but be not limited to as copper alloy plate as long as there is the characteristic, the shape of copper alloy plate
Sheet material or web.In the present invention, tubing also may be interpreted as sheet material and be used.
[area occupation ratio of Cube orientations]
In order to improve the bendability of copper alloy plate, the present inventor is waited for the slight crack in bending machining portion occurs
Occurrence cause is investigated.Results verification arrives, the reason for this is that：Plastic deformation locally develops and forms Shear heating instability,
The generation and link of micropore (micro void) because of the processing hardening of part, so as to reach forming limit.As its countermeasure,
It was found that the ratio that the crystal orientation for being not susceptible to processing hardening is improved in flexural deformation is effective.That is, find thick in sheet material
Spend in the crystal orientation analysis of the EBSD measure in direction, when Cube is orientated { 001 }<1 0 0>Area occupation ratio be 5%~50%
When, good bendability is shown, the present invention is completed based on this opinion.Cube orientation area occupation ratio for above-mentioned lower limit with
When upper, above-mentioned action effect can be given full play to.Also, below above-mentioned higher limit, then it can not be carried out with low working modulus
Cold calendaring processing after recrystallization processing, intensity will not significantly reduce, therefore preferably.From the above point of view, Cube is orientated
{0 0 1}<1 0 0>Area occupation ratio preferred scope be 7%~47%, more preferably 10%~45%.
[orientation beyond Cube orientations]
In addition, in addition to the Cube orientations of above range, S orientations { 231 } can be produced<3 4 6>, Copper orientation
{1 2 1}<1 1 1>, D orientation { 4 11 4 }<11 8 11>, Brass orientation { 110 }<1 1 2>, Goss orientation { 110 }
<0 0 1>, R1 orientation { 352 }<3 5 8>, RDW orientation { 102 }<0 1 0>Deng.In the present invention, as long as Cube is orientated
Relative to the area occupation ratio for the area being all orientated observed in above range, then allow to include these orientation components.
[EBSD methods]
The method for expressing of crystal orientation in this specification is as follows：Use with the length direction of copper alloy plate (LD) { etc.
It is same as the rolling direction (RD) of sheet material } it is X-axis, be Y-axis with plate width direction (TD), sheet material { is equal to the thickness direction of sheet material
Calendering normal direction (ND) be Z axis rectangular coordinate system, in each region in copper alloy plate, using vertical with Z axis
Index [the u of the index (h k l) of the crystal face of (parallel with calendering face (XY faces)) and the crystal face of (parallel with YZ faces) vertical with X-axis
V w], represented in the form of (h k l) [u v w].In addition, such as (1 3 2) [6-4 3] and (23 1) [3-4 6] etc.,
On equivalent orientation on the basis of the symmetry of the cubic crystal of copper alloy, using the bracket mark for representing family, { h is expressed as
k l}<u v w>。
The analysis of above-mentioned crystal orientation in the present invention employs EBSD methods.So-called EBSD is Electron
Backscatter Diffraction (EBSD) abbreviation, it is make use of in sweep electron microscope
(SEM) to the crystal orientation analytical technology of Kikuchi lines RED reflection electron diffraction caused by sample irradiation electron ray in.In the present invention, with
0.5 micron etc. of stride is scanned to the sample area of 1 micrometre square containing more than 200 crystal grain, and analyzes orientation.
Determining area and scanning stride is adjusted according to the crystallite dimension of sample.The area occupation ratio being respectively orientated is from Cube orientations { 00
1}<1 0 0>Desirable orientation play ratio of the area within ± 10 ° relative to total measure area.Utilize EBSD orientation analysis
The packet of gained invades the orientation information of the number 10nm of sample depth containing electron ray, but due to much smaller than measure
Scope, therefore area occupation ratio is recited as in this manual.Further, since distribution of orientations can be varied from thickness of slab direction, therefore
Orientation analysis using EBSD is preferably arbitrarily to choose several points in thickness of slab direction and average.
The so-called area occupation ratio being respectively orientated refers to, is the region within 10 ° by the deviation angle from each ideal orientation
Value obtained by area divided by measure area.
On the deviation angle from ideal orientation, centered on shared rotary shaft, the anglec of rotation is calculated, as inclined
Digression degree.Fig. 1 show from Cube orientation deviation angle be 10 ° within orientation example.Herein, though it is shown that closing
Orientation within 10 ° of the rotary shaft of (100), (110) and (111), but can be from any rotary shaft calculating and Cube
The anglec of rotation of orientation.Rotary shaft uses rotary shaft that can be with the deviation angle of minimum to represent, for all measuring points
Calculate the deviation angle, using the area of the crystal grain with the orientation within from each orientation 10 ° and divided by total measure area as
Area occupation ratio.
The number 10nm of sample depth is invaded containing electron ray using the packet that EBSD orientation analysis is obtained
Orientation information, but due to the scope much smaller than measure, therefore usable floor area rate in this manual.Distribution of orientations is closed from copper
What the plate surface of golden plate material was measured, when distribution of orientations is varied from thickness of slab direction, utilize EBSD orientation analysis
For arbitrarily chosen in thickness of slab direction several points, carry out averagely after obtained from value.
Herein, the feature of EBSD measure is illustrated using the mode of the contrast with X-ray diffraction measure.
First, enumerate for the 1st point, can only be determined using the method for X-ray diffraction and be met Prague (Bragg)
Diffraction conditions and this 5 kinds of ND//(111), (200), (220), (311), (420) face of sufficient diffracted intensity can be obtained, it is right
It is 15 °~30 ° in the deviation angle being orientated from Cube to show with high index such as ND//(511) face or ND//(951) face
Crystal orientation can not then determine.That is, determined by using EBSD, obtain the crystal represented on these with high index first
The information of orientation, specific metal structure is thus set to be apparent with the relation acted on.
2nd point, X-ray diffraction is measured to the component of ND//{ hkl } ± 0.5 ° or so the crystal orientation included,
In contrast, EBSD measure is to utilize Kikuchi style, therefore specific crystal face is not only restricted to, obtained with can covering and metal group
The quite extensive information of correlation is knitted, specify that the state for being integrally difficult to be determined by X-ray diffraction as alloy material.
As described above, determined by EBSD different with its content of the information obtained by X-ray diffraction measure and property.
It should be noted that in this specification unless otherwise specified, then EBSD measure is relative to copper alloy plate
ND directions and carry out.
[X-ray diffraction intensity]
In the present invention, the X-ray diffraction intensity in { 200 } face from alloy surface is set to I { 200 }, from fine copper
The X-ray diffraction intensity in { 200 } face of standard powder is set to I0When { 200 }, preferably meet following (a) formula, further preferably tool
There is the crystalline orientation for meeting following (b) formula.
I{200}/I0{ 200 } >=1.3 formula (a)
I{200}/I0{ 200 } >=2.5 formula (b)
[Ti]
In the present invention, the addition of copper (Cu) titanium (Ti) is made an addition to by control, can separate out Cu-Ti compounds,
So as to lift the intensity of copper alloy.Ti content is the matter of 1.0 mass %~5.0 mass %, preferably 2.0 mass %~4.0
Measure %.If the addition of the element is more than this prescribed limit, conductance can be reduced；In addition, if addition is advised less than this
Determine scope, then intensity deficiency.It should be noted that the copper alloy as the present invention is contained into Ti as the second alloy sometimes
The material of composition is referred to as [Ti series copper alloys].
[secondary addition element]
Secondly, the effect of the secondary addition element of this alloy is shown.As preferable secondary addition element, can enumerate Sn,
Zn, Ag, Mn, B, P, Mg, Cr, Zr, Si, Fe and Hf.For the content of these secondary addition element, if selected from by Sn, Zn, Ag, Mn,
B, the total amount of at least one kind of element in the group of P, Mg, Cr, Zr, Si, Fe and Hf composition is below 1 mass %, then will not produce and lead
The shortcomings that causing conductance to decline, thus preferably.In order to fully apply flexibly additive effect, and decline conductance, these pair additions
The content of element is preferably calculated as the mass % of 0.005 mass %~1.0 with total amount, the matter of more preferably 0.01 mass %~0.9
Measure %, the mass % of particularly preferably 0.03 mass %~0.8.Hereinafter, the example of the additive effect of each element is shown.
(Mg、Sn、Zn)
Stress relaxation-resistant characteristic can be lifted by adding Mg, Sn, Zn.Compared with situation about each individually adding, add in the lump
Situation can further lift stress relaxation-resistant characteristic because of multiplication effect.Also have in addition and significantly improve the brittle effect of welding
Fruit.
(Mn、Ag、B、P)
If adding Mn, Ag, B, P, hot-workability can be improved, while lift intensity.
(Cr、Zr、Si、Fe、Hf)
Cr, Zr, Si, Fe, Hf can imperceptibly be separated out in the form of compound or simple substance, and help to be hardened by precipitation.In addition,
Separated out in the form of compound with 50nm~500nm size, suppress crystal grain-growth, thus having makes the fine effect of crystallization particle diameter
Fruit, and bendability is become good.
[manufacture method of copper alloy plate]
Then, the preferably fabricated condition of the copper alloy plate of the present invention is illustrated.
In the manufacture method of conventional precipitation type copper alloy, [process 1] is cast to copper alloy raw material and obtains ingot bar, then
After the heat treatment that homogenizes [process 2] is imposed to it, hot calender [process 3], water cooling [process 4], surface cut [process are sequentially carried out
5], cold calendaring [process 6] makes its thin plate, the solutionizing heat treatment [work among 700 DEG C~1000 DEG C of temperature ranges are carried out
Sequence 9] and make after solute atoms is dissolved again, being heat-treated [process 10] and cold sperm calendering [process 11] by Precipitation makes it full
The necessary intensity of foot.In this series of process, on the set tissue of copper alloy, its major part is by middle solutionizing heat
Handle caused recrystallization in [process 9] and determine, and by pressure-sizing prolong the rotation of caused orientation in [process 11] Lai
Determine its last state.
Relative to above-mentioned conventional method, in an embodiment of the invention, in hot calender [process 3] laggard water-filling
Cold [process 4], surface cut [process 5], and calendering rate more than 80% and less than 99.8% pressure are carried out with cold calendaring [process 6]
Prolong, thereafter, in the degree not recrystallized, after being heated to 600 DEG C~800 DEG C with 10 DEG C/sec~30 DEG C/sec of programming rate,
Carry out with more than the 200 DEG C/sec intermediate annealings rapidly cooled down [process 7], and it is 2%~50% further to carry out working modulus
Cold calendaring [process 8], thus middle solutionizing heat treatment [process 9] recrystallization set tissue in, Cube orientation face
Product rate increased.In addition, middle solutionizing be heat-treated [process 9] after, can also implement Precipitation heat treatment [process 10],
Cold sperm rolls [process 11] and quenched annealing [process 12].
A preferred embodiment for setting each operation condition in more detail is recorded below.
Copper alloy raw material is melted using high frequency smelting furnace, and the copper alloy raw material is according at least containing 1.0 mass %~5.0
Quality % Ti has simultaneously suitably carried out the mixture of element containing the modes of other above-mentioned secondary addition element, and remainder is then by Cu
Formed with inevitable impurity, to it so that 0.1 DEG C/sec~100 DEG C/sec of cooling velocity is cast [process 1] and is obtained
Ingot bar.After carrying out the heat treatment that homogenizes [process 2] of 3 minutes~10 hours to ingot bar with 800 DEG C~1020 DEG C, with 1020 DEG C~
700 DEG C carry out hot-working [process 3], then carry out water quenching (equivalent to water cooling [process 4]).Afterwards, can also carry out as needed
Surface cut [process 5] is with scale removal.Then, the cold calendaring [process 6] that rate is 80%~99.8% is processed, then
Heated with 10 DEG C/sec~30 DEG C/sec of programming rate, after reaching 600 DEG C~800 DEG C, carried out with 200 DEG C/sec with enterprising
The intermediate annealing [process 7] that row rapidly cools down, rate is further processed as 2%~50% cold calendaring [process 8], and with
600 DEG C~1000 DEG C middle solutionizing heat treatments [process 9] for carrying out 5 seconds~1 hour.Afterwards, 400 DEG C~700 can also be carried out
DEG C, the heat treatment of the Precipitation of 5 minutes~10 hours [process 10], the cold sperm that working modulus is 3%~25% roll [process 11],
200 DEG C~600 DEG C and 5 seconds~10 hours of quenched annealing [process 12].The copper that the present invention can be obtained according to above method closes
Golden plate material.
In the present embodiment, in hot calender [process 3], carried out in 700 DEG C from relation reheating temperature of temperature provinces
For destroying cast sturcture or segregation to obtain the processing of uniform formation and for making crystal grain miniaturization by dynamic recrystallization
Processing.In intermediate annealing [process 7], after being heat-treated under the degree that the tissue in not making alloy recrystallizes comprehensively,
The cold calendaring [process 8] that rate is 2%~50% is processed, makes Cube in the recrystallization set tissue of middle solid solution [process 9]
The area occupation ratio increase of orientation.Herein, if make the intermediate annealing [process 7] before middle solutionizing [process 9] is heat-treated to Da Wen
Degree can then form oxide skin, not to be preferred, therefore by the heat treatment of the intermediate annealing [process 7] higher than the setting of the present invention
Reach temperature and be set as 600 DEG C~800 DEG C.Wherein, though being difficult to unambiguously conclude, by intermediate annealing [process 7]
In specify be annealed to up to temperature and the working modulus of cold calendaring [process 8] be adjusted, Cube orientation area occupation ratio have it is increased
Tendency.That is, in intermediate annealing [process 7], it is not kept at and is annealed to up to temperature but is heated with defined programming rate,
When reaching after being annealed to up to temperature of target, cooled down at once with defined cooling velocity.
Herein, if the liter temperature Rate of intermediate annealing [process 7] is slower than 10 DEG C/sec, crystal grain-growth, coarse grains are caused
Change, bending gauffer becomes big.If programming rate is faster than 30 DEG C/sec, Cube orientations are underdeveloped, and bendability is not good enough.This
Outside, the situation that temperature is less than 600 DEG C is reached, Cube orientations will not develop, and bendability is not good enough；Situation higher than 800 DEG C, it is brilliant
Grain growth, causes coarse grains, and bending gauffer becomes big and makes deterioration in characteristics.In addition, as noted above it is believed that implement such as working modulus
Force work for 80%~99.8% cold calendaring [process 6], may result in thick crystal, precipitate caused by casting
Around occur indexing, strain, and make Cube orientation growth middle solutionizing heat treatment [process 9] in hinder orientation revolve
Turn, but by implementing intermediate annealing [process 7], indexing, strain herein can be liberated, therefore middle solutionizing heat can be suppressed
Handle the obstruction of the Cube orientation growth in [process 9].
Then, cold calendaring [process 8] is implemented with 2%~50% working modulus.Herein, if working modulus is less than 2%, process
It should diminish, be heat-treated crystallization particle diameter meeting coarsening in [process 9] in middle solutionizing, bending gauffer can become big and owe characteristic
It is good.If working modulus can not fully develop higher than 50%, Cube orientations, bendability is not good enough.
After middle solutionizing is heat-treated [process 9], implement Precipitation heat treatment [process 10], cold sperm calendering [work
Sequence 11], it is quenched annealing [process 12].Herein, the treatment temperature of Precipitation heat treatment [process 10] is less than middle solutionizing heat
Handle the treatment temperature of [process 9].In addition, the treatment temperature of quenched annealing [process 12] is less than middle solutionizing heat treatment [work
Sequence 9] treatment temperature.
In order to gather the area occupation ratio increase for being orientated Cube in tissue in recrystallization, cold sperm processing [process 11] is carried out.And
And assist the development that Cube is orientated by the way that crystal orientation is controlled in into certain orientation.
More processing strains are introduced by cold calendaring [process 6], and apply programming rate in intermediate annealing [process 7]
10 DEG C/sec~30 DEG C/sec, reach 600 DEG C~800 DEG C of temperature, reach after the heat treatment that rapidly cools down, thus in middle solutionizing
Make Cube orientation area occupation ratio increases in recrystallization set tissue caused by heat treatment [process 9].In intermediate annealing [process 7],
Do not recrystallized completely, its purpose is to obtain the partial annealing tissue of partial, re-crystallization.In cold calendaring [process
8] in, the purpose is to the calendering for being 2%~50% by working modulus to import microcosmic uneven strain.Pass through intermediate annealing
The action effect of [process 7] and cold calendaring [process 8], it may be such that the Cube in middle solutionizing heat treatment [process 9] is orientated to
It is long.Generally, the heat treatment as middle solutionizing heat treatment [process 9], its main purpose is to reduce subsequent processing
Bear and make copper alloy plate recrystallization to reduce intensity, but it is simultaneously different from this purpose in the present invention.
Working modulus (also referred to as reduction ratio, section slip in above-mentioned each calendering procedure.Described in following comparative example
Calendering rate is also identical meaning.) refer to use the thickness of slab t before calendering procedure1With the thickness of slab t after calendering procedure2, counted by following formula
The value calculated.
Working modulus (%)=((t1-t2)/t1)×100
Also it can as needed carry out removing the surface cut of the oxide skin of material surface, be carried out in a manner of pickling etc.
Dissolving.When shape after calendering is not good enough, it can also be corrected as desired by tension leveler etc..
In addition, after each heat treatment or calendering, as long as Cube orientations { 001 }<1 0 0>Area occupation ratio the present invention
In the range of, then pickling or surface grinding can be carried out according to the oxidation of material surface or the state of roughness or be utilized according to shape
Tension leveler is corrected.
[characteristic of copper alloy plate]
By meeting the above, the characteristic for example required by copper alloy for connector use sheet material can be met.In the present invention
In, copper alloy plate preferably has following characteristics.
0.2% yield strength is preferably more than 850MPa.More preferably more than 950MPa.For 0.2% surrender
The higher limit of intensity is not particularly limited, but generally below 1000MPa.For detailed condition determination as long as no especially saying
It is bright, then as described embodiments.
Bendability is preferably capable carrying out bending flawless and that bending gauffer is small in 90 ° of W bend tests and added
Value (r/t) obtained by the minimum bending radius (r) divided by thickness of slab (t) of work is less than 1.On bending gauffer, preferably bending is wrinkled
Gauffer spacing is less than 20 μm when pleat is GW, and gauffer spacing is less than 25 μm when bending gauffer is BW.During more preferably GW
Gauffer spacing below 15 μm, when being BW below 20 μm.For detailed condition determination unless otherwise specified, then such as
Described in embodiment.Herein, in the experiment material cut out perpendicular to rolling direction, at a right angle according to axle and the rolling direction of bending
The situation that mode carries out W bendings is referred to as GW (Good Way), and carries out W into parallel mode with rolling direction according to the axle of bending
The situation of bending is referred to as BW (Bad Way).
Conductance is preferably more than 5%IACS.More preferably conductance is more than 10%IACS.For conductance
Higher limit have no particular limits, but usually below 30%IACS.For detailed condition determination as long as no especially saying
It is bright, then as described embodiments.
Young's modulus is preferred in 80GPa~110GPa in 90GPa~120GPa, bending coefficient.More preferably
Young's modulus is 100GPa~110GPa, bending coefficient is 90GPa~100GPa.For detailed condition determination as long as no spy
Do not mentionlet alone it is bright, then as described embodiments.
Stress relaxation-resistant characteristic can realize less than 5% superperformance by the present invention.For detailed measure bar
Part unless otherwise specified, then as described embodiments.
[embodiment]
Hereinafter, the present invention is illustrated according to embodiment in further detail, but the present invention is not limited to these embodiments.
(embodiment 1)
On example 1 of the present invention~example of the present invention 21,1~comparative example of comparative example 17, the Cu and Ti of mixture main material, and foundation
The other secondary addition element of test example mixture and as the composition shown in table 1, melted, cast.
That is, using high frequency smelting furnace to Ti containing the amount shown in table 1 etc. and remainder is by copper and inevitable impurity
The alloy of composition is melted, to it so that 0.1 DEG C/sec~100 DEG C/sec of cooling velocity is cast [process 1] and is cast
Block.After carrying out the heat treatment that homogenizes [process 2] of 3 minutes~10 hours to ingot bar with 800 DEG C~1020 DEG C, with 1020 DEG C~
700 DEG C carry out hot-working [process 3].Then, water quenching (equivalent to water cooling [process 4]) is carried out, and for scale removal, is entered
Surface cut [process 5] is gone.Thereafter, the cold calendaring [process 6] that rate is 80%~99.8% is processed, then with the speed that heats up
10 DEG C/sec~30 DEG C/sec heating of degree, after reaching 600 DEG C~800 DEG C, are carried out with the intermediate annealing [work of more than 200 DEG C/sec chillings
Sequence 7], further implement the cold calendaring [process 8] of 2%~50% working modulus, 600 DEG C~1000 DEG C and 5 seconds~1 hour
Middle solutionizing is heat-treated [process 9].Secondly, it is heat-treated with 400 DEG C~700 DEG C Precipitations for carrying out 5 minutes~1 hour
[process 10], and carry out cold sperm calendering [process 11], 200 DEG C~600 DEG C and 5 seconds~10 hours that calendering rate is 3%~25%
Quenched annealing [process 12], and experiment material is made.As shown in table 2, in a comparative example, intermediate annealing [process 7] and cold calendaring
[process 8] is implemented beyond above-mentioned condition.On example of the present invention and comparative example, table 1, table 2 show these experiment materials composition,
Condition and resulting characteristic of the intermediate annealing [process 7] with cold calendaring [process 8].After each heat treatment or calendering, according to material
The oxidation on surface or the state of roughness carry out pickling or surface grinding, and are corrected according to shape using tension leveler.Need
It is noted that the processing temperature of hot-working [process 3] is the radiation temperature by being arranged on calender porch and exit
Measure.
Following characteristic surveys have been carried out to these experiment materials.Herein, the thickness for testing material is set as 0.15mm.Evaluation result
It is shown in table 2.
A.Cube is orientated the area occupation ratio with S orientations
Using EBSD methods, to determine area as 0.08 μm2~0.15 μm2, scanning stride be 0.5 μm~1 μm condition carry out
Measure.Measure area is adjusted on the basis of the crystal grain containing more than 200.Scanning stride is adjusted according to crystallization particle diameter
It is whole, in the case that average crystal grain footpath is below 15 μm, carried out with 0.5 μm of stride；And in the case of less than 30 μm, then with 1 μm of step
Width is carried out.The thermoelectron of the tungsten filament of self-scan type electron microscope is as occurring source since electron ray.
Measure device as EBSD methods uses the OIM5.0 (trade name) that (strain) TSL Solutions are manufactured.
B. bendability
Wide 10mm, long 35mm test film are vertically cut out with rolling direction, by its with the axle of bending perpendicular to calendering
The mode in direction carries out the situation of W bendings as GW (Good Way), and W is carried out in a manner of the axle of bending is parallel to rolling direction
The situation of bending is as BW (Bad Way), and with 50 times of observation by light microscope crooked position, investigation has flawless.Will be without splitting
The judgement of trace is zero (" good "), crackled, is determined as × (" poor ").The angle of bend of each crooked position is set as 90 °, respectively
The inner radius of crooked position is set as 0.15mm.To impose a condition as minimum bending radius (r) be 0.15mm, thickness of slab (t) is
0.15mm, it is 1 than (r/t).
C. the judgement of gauffer is bent
To the bending gauffer of the bending machining portion faces of the sample after 90 ° of W bend tests, 180 ° of closely sealed bend tests
Judged.Resin edge is carried out to sample to bury, and bending sections are observed with SEM.The size of gauffer is seen by cross-section
Gauffer ditch and ditch between size determine.On bending gauffer, if gauffer spacing is at 20 μm when bending gauffer is GW
Below, when being BW below 25 μm, then it is qualified to be determined as.
D.0.2% yield strength [YS]
According to JIS Z2241,3 JIS Z2201-13B cut out from calendering parallel direction of measure test film, represent
Its average value.
E. conductance [EC]
In the thermostat for being held in 20 DEG C (± 0.5 DEG C), resistivity is measured with four-terminal method so as to calculate conductance.
In addition, distance is set to 100mm between terminal.
F. Young's modulus
Wide 20mm, long 150mm test film are cut out from calendering parallel direction, it is to exist per 50mm to be processed into the depth of parallelism
Below 0.05mm.Young's modulus represents the value calculated by the gradient of the Hookean region of the stress-strain curve of tension test.
G. bending coefficient
Test film is cut out from calendering parallel direction, makes width be 10mm according to Japanese Shen Tong associations technical standard, thickness of slab is
0.1mm~0.65mm, more than 100 times that length is thickness of slab.According to JIS H 3130, the surface of each test piece is distinguished with the back side
The gradient of Hookean region, represents its average value in stress-strain line chart when measure bends 2 times beam arm (cantilever).
H.X ray diffraction intensities
One axial diffracted intensity of rotation of sample is measured with bounce technique.Target uses copper, and uses K α
X ray.It is measured with tube current 20mA, tube voltage 40kV condition, in the figure of the angle of diffraction and diffracted intensity, is removed
After the background value of diffracted intensity, the integrated diffraction intensity for being added together the K α 1 of each crest and K α 2 is tried to achieve, so as to obtain I
{ 200 } and I0{ 200 } diffracted intensity is than I { 200 }/I0{200}。
I. stress relaxation rate [SRR]
According to former days this electronic material industry can standard specification (EMAS-3003), it is as follows, it is small with 150 DEG C × 1000
When condition be measured.Apply 80% primary stress of yield strength with cantilever method.
Fig. 2 is the explanation figure of the test method of stress relaxation-resistant characteristic, and Fig. 2 (a) is the state before heat treatment, and Fig. 2 (b) is
State after heat treatment.As shown in Fig. 2 (a), apply yield strength for the test film 1 for being maintained at testboard 4 in cantilever fashion
80% primary stress when, there is δ the position of test film 1 from benchmark0Distance.It is set to be kept in 150 DEG C of thermostat
1000 hours, shown in position such as Fig. 2 (b) of the test film 2 after elimination capacity, there is H from benchmarktDistance.3 be not bear to answer
There is H test film during power, its position from benchmark1Distance.Thus relation, it is (H to calculate stress relaxation rate (%)t-H1)/
δ0×100。
It is it should be noted that also applicable as same test method, following method：Japanese Shen Tong associations (JCBA：
Japan Copper and Brass Association) technical standard scheme " JCBA T309：2001 (tentative)；Based on copper
And the stress relaxation test method of the bending progress of copper alloy thin plate bar "；American Society for Testing Materials (ASTM；American
Society for Testing and Materials) test method " ASTM E328；Standard Test Methods
for Stress Relaxation Tests for Materials and Structures”；Deng.
Fig. 3 is according to above-mentioned JCBA T309：The flexing displacement of musical form cantilever bolt type is scratched in 2001 (tentative), use lower section
Load carries out the explanation figure of stress relaxation test method with test fixture.The principle of the test method and the testing stand using Fig. 2
Test method it is identical, therefore stress relaxation rate is also almost same value.
In the method for testing, test film 11 is arranged on test fixture (experimental rig) 12 first, given at room temperature
Defined displacement is given, elimination capacity after being kept for 30 seconds, using the bottom surface of test fixture 12 as reference plane 13, determines this face 13 and examination
Test the distance between flexural loads point of piece 11 and be used as Hi.After the defined time, experiment is taken out from thermostat or heating furnace
Fixture 12 is placed in normal temperature, unclamps the flexural loads elimination capacity of bolt 14.After test film 11 is cooled into normal temperature, reference plane is determined
13 with the distance between the flexural loads point of test film 11 Ht.After measure, flexing displacement is given again.It should be noted that figure
In, 11 represent test film during elimination capacity, and 15 represent test film during flexural loads.Permanent deflection displacement δtAsk according to the following formula
.
δt=Hi-Ht
Stress relaxation rate (%) is calculated as δ with this relationt/δ0×100。
It should be noted that δ0It is in order to obtain the flexing displacement at initial stage of the test film needed for defined stress, with following formula
Calculate.
δ0=σ 1S 2/1.5Eh
Herein, σ：Surface maximum stress (the N/mm of test film2)；h：Thickness of slab (mm)；E：Bending coefficient (N/mm2)、1S：Across
Away from (ス パ Application) length (mm).
As shown in table 2, in the manufacture method of example 1 of the present invention~example of the present invention 21, intermediate annealing [process 7] is to heat up
Speed is 10 DEG C/sec~30 DEG C/sec, reaches temperature be 600 DEG C~800 DEG C and temperature reach after with chilling (the cooling speed of water quenching
Spend for more than 200 DEG C/sec) be heat-treated.Afterwards, cold calendaring [process 8] processing of 2%~50% working modulus is applied.
In 1~comparative example of comparative example 17, the defined situation for being unsatisfactory for the manufacture method of the present invention is shown.Comparative example 5,6,16,
In 17, Ti compositions are outside scope；In the intermediate annealing [process 7] of 1~comparative example of comparative example 17, comparative example 1,4,6,8,11,12,
16th, 17 programming rate is outside scope；In comparative example 3~6,10,11,14~17, temperature is reached outside scope.In addition,
In comparative example 2,6,7,9,12,13,15~16, the working modulus of cold calendaring [process 8] is outside scope.In addition, as shown in table 1,
In comparative example 10, the addition of third element is excessive, beyond 0.005%~1.0% scope as setting.
As shown in table 2, in example 1 of the present invention~example of the present invention 21, bendability, yield strength are excellent.However, such as compare
Shown in 1~comparative example of example 17, in the case of being unsatisfactory for as defined in the present invention, its result is that characteristic is not good enough.Example 1 of the present invention~sheet
Example 21 promotes the crystal orientation of titanium copper to rotate by being heat-treated in the temperature province less than solid solubility temperature, final big
Cube orientation area occupation ratios are improved width, improve bendability.In example 1 of the present invention~example of the present invention 21, Cube orientation be 5% with
On.The bending machining surface portion gauffer of example 1 of the present invention~example of the present invention 21 is GW≤20 μm, the size of BW≤25 μm, is not had
Slight crack and bending gauffer is small, therefore excellent in bending workability.In addition, Young's modulus and bending coefficient are also within the limits prescribed.
On the other hand, in comparative example 1~7, comparative example 9,10, comparative example 12~14, comparative example 16,17, curved surface
Generate slight crack.The Cube of comparative example 1~17 is orientated area occupation ratio outside the scope of setting 5%~50%.Wherein, Cube takes
In the comparative example 5 low to area occupation ratio, bendability is not good enough；In the high comparative example 8 of Cube orientation area occupation ratios, yield strength is owed
It is good.
In comparative example 1~17, in addition to comparative example 8, comparative example 11, X-ray diffraction integrated intensity is than I { 200 }/I0
{ 200 } less than the 1.3 of setting.Comparative example 8, the display of comparative example 11 more than 1.3, but yield strength is not good enough.
The Ti contents of comparative example 5,6,16,17 are outside the scope as setting 1.0%~5.0%.
In 1~comparative example of comparative example 17, the programming rate of intermediate annealing, arrival temperature, cold calendaring working modulus are providing
Outside the scope of value, characteristic is also outside defined scope.In comparative example 1, comparative example 3, comparative example 4, comparative example 7~9, comparative example
11st, in comparative example 13~17, Young's modulus is outside the scope as setting 90GPa~120GPa.In addition, in comparative example 1, ratio
Compared with example 3~8, comparative example 10~11, comparative example 13~17, bending coefficient is in the scope as setting 80GPa~110GPa
Outside.In addition, in comparative example 10, the addition of third element is more compared with setting, and conductance reduces；In comparative example 14, third element
Addition it is few compared with setting, the arrival temperature of intermediate annealing is too high, therefore causes to produce slight crack and gauffer in bending machining,
Yield strength (intensity) is low, and Young's modulus is too high with bending coefficient.Although comparative example 15 can be in the case of GW, BW be crackless
Bending, yield strength also meets setting, but the gauffer of bending machining surface portion is big, and Young's modulus, bending coefficient are also all super
Go out the upper limit of setting, characteristic is not good enough.In comparative example 16,17, Ti content, manufacturing process are outside prescribed limit, Cube
Orientation area occupation ratio, I { 200 } diffracted intensity are also outside defined scope.
In comparative example 3~6,9,14~17, Cube orientation area occupation ratio outside scope, and without addition element (to
Improve stress relaxation-resistant characteristic), as a result compared with example 1~21 of the present invention, stress relaxation-resistant characteristic is not good enough.
In the present invention, by controlling the programming rate of intermediate annealing [process 7], reaching temperature, cold calendaring [process 8]
Working modulus obtains destination organization, has bendability and intensity concurrently, can further be met bending machining surface portion
Gauffer size, Young's modulus, the CTB alloy sheet material of bending coefficient.
(past case)
(remainder is copper (Cu)) is formed for the alloy that Table 3 below is recorded, except without intermediate annealing [process 7]
Beyond cold calendaring [process 8] thereafter, by with above-described embodiment 1 it is same in a manner of make copper alloy plate.To the copper of acquisition
The experiment material of sheet alloy, is evaluated in the method same with above-described embodiment 1.Its result is shown in table 3 in the lump.
As shown in Table 3, without intermediate annealing [process 7] and the past case 1 made by cold calendaring [process 8] thereafter~
Although 3 copper alloy plate employs defined alloy composition and manufacturing condition (each operation and the bar beyond the two processes
Part), but no matter any copper alloy plate, its Cube orientations area occupation ratio less and bendability is not good enough, have slight crack produce or
There is obvious big gauffer to produce.
This is different from, in order to clearly use the copper alloy plate and the copper alloy of the present invention manufactured by conventional manufacturing condition
Difference between sheet material, copper alloy plate is made with the conventional manufacturing condition, carries out commenting for characteristic project same as described above
Valency.If it is that adjustment working modulus becomes and above-mentioned reality it should be noted that being not particularly illustrated for the thickness of each sheet material
Apply an identical thickness.
The condition of (comparative example 101) Japanese Unexamined Patent Publication 2011-26635 publications example 1 of the present invention
Melting manufacture is carried out to forming the copper alloy being made up of for the Ti containing 3.25 mass % and remainder Cu, and is made
Cast with longitudinal type semicontinuous casting machine.
The slab of gained is heated to 950 DEG C, temperature is down to 400 DEG C from 950 DEG C while carry out hot calender, is made
After thickness about 9mm sheet material, rapidly cooled down with water cooling, then, the oxidation on (surface cut) top layer is removed with mechanical lapping
Layer.The relation that the thickness of the sheet material is depended between the calendering rate of each cold calendaring thereafter and last thickness of slab.Then, with 84%
After calendering rate carries out the first cold calendaring, implement intermediate annealing process.Intermediate annealing (heat treatment) is carried out 6 hours with 550 DEG C.Respectively
Conductance before and after intermediate annealing is set to Eb and Ea, respective Vickers hardness is set to Hb and Ha, Ea/Eb 3.3, and Ha/Hb
For 0.72.Afterwards, the second cold calendaring has been carried out with 86% calendering rate.
Then, formed according to alloy, keep carrying out solutionizing processing in 15 seconds at 900 DEG C, make calendering plate surface (according to JIS
The H0501 process of chopping) average crystallite particle diameter be more than 5 μm and below 25 μm.
Thereafter calendering, which is omitted, among is not carried out.
Then, with 450 DEG C of progress Ageing Treatments.Aging time is to be formed and be adjusted at 450 DEG C according to copper alloy
Timeliness under hardness can reach time of peak value.It should be noted that for the aging time, according to example 1 of the present invention
Alloy is formed, and optimal aging time is tried to achieve by pilot study.
Then, for the sheet material after above-mentioned Ageing Treatment, cold sperm calendering is further imposed with 15% calendering rate.Also,
Implement the process annealing that the retention time is 1 minute in the annealing furnace of 450 DEG C of furnace temperature.In addition, as needed, ground halfway
Mill, surface cut, make thickness of slab be unified for 0.10mm.
Sample c01 is used as using it.
For the test body c01 of gained, it is different from embodiments of the invention described above in terms of manufacturing condition
Between the treatment temperature that makes annealing treatment it is low and processing time is grown, and the calendering rate of the second cold calendaring after the intermediate annealing process
Greatly；Its result is that Cube orientations are less than 5%, and the bendability for rolling vertical direction fails the requirement characteristic for meeting the present invention.
The condition of (comparative example 102) Japanese Unexamined Patent Publication 2010-126777 publications embodiment 1
To forming the copper alloy being made up of for the Ti containing 3.18 mass % and remainder Cu there is melting to manufacture, and make
Cast with longitudinal type semicontinuous casting machine, obtain the slab that thickness is 60mm.
Taken out after the slab is heated into 950 DEG C, carry out hot calender.In the hot calender, setting pass schedule makes 750
The calendering rate of temperature province more than DEG C is more than 60% and can also rolled in the temperature province not up to 700 DEG C.In addition,
Hot calender rate less than 700 DEG C~500 DEG C is set as 42%, the final passage temperature of hot calender be set as 600 DEG C~500 DEG C it
Between.In addition, it is about 95% by total hot calender rate slab.After hot calender, (surface cut) top layer is removed with mechanical lapping
Oxide layer.
Then, after carrying out the cold calendaring that calendering rate is 98%, solutionizing processing is carried out.In solutionizing processing, according to
Its alloy form in be set in 750 DEG C~1000 DEG C of temperature province than the alloy composition liquidoid be higher by more than 30 DEG C
Temperature, and the retention time was adjusted to be heat-treated in the range of 5 seconds~5 minutes, make the average crystallite after solutionizing processing
Particle diameter (twin boundary is not intended as crystal boundary) is 5 μm~25 μm.Specifically, the heat treatment of 15 seconds is carried out at 900 DEG C.
Then, the sheet material after handling solutionizing bestows the cold calendaring that calendering rate is 15%.
The timeliness of most long to 24 hours within the temperature range of 300 DEG C~550 DEG C is carried out for the sheet material obtained in this way
Processing experiment is used as preliminary experiment, so as to grasp the Ageing conditions (aging temp up to highest hardness according to alloy composition
TM(DEG C), aging time tM(minute), highest hardness HM(HV)).Then, aging temp is set as in TM± 10 DEG C of scope
Interior temperature, while aging time is set as to compare tMHardness after short and timeliness is 0.90HM~0.95HMScope time.
Then, after the cold sperm calendering that calendering rate is 10% is carried out to the sheet material after Ageing Treatment, it is carried out at 450 DEG C of annealing
The process annealing of 1 minute is kept in stove.
Copper alloy plate is obtained in the above described manner.In addition, as needed, surface cut is carried out in midway, makes copper alloy plate
The thickness of slab of material is unified for 0.15mm.As sample c02.
For the test body c02 of gained, it is heat in terms of manufacturing condition with the difference of embodiments of the invention described above
Calendering is carried out with two benches, and do not carry out the intermediate annealing [process 7] of solutionizing before processing and cold calendaring [process 8] and
Solutionizing processing is directly carried out, the heat treatment after cold calendaring [process 6] is different from the process of cold calendaring；Its result is,
Cube orientations are less than 5%, and the bendability for rolling vertical direction fails the requirement characteristic for meeting the present invention.
Although the present invention is illustrated together with embodiments thereof, unless we have it is special specify, otherwise I
Be not intended to the present invention is limited in any details of explanation, the present invention should not depart from the application claims
Can broad interpretation in the case of shown spirit and scope.
The priority based on the Japanese Patent Application 2010-195120 to be filed an application in Japan on the 31st of August in 2010 is advocated in this case,
Entire contents are herein incorporated by reference as a part of content that this specification is recorded.
Claims (7)
1. a kind of copper alloy plate, its be containing 1.0 mass %~5.0 mass % Ti, remainder is by copper and inevitable
The copper alloy plate that forms of impurity, the copper alloy plate is characterised by, in the crystal orientation analysis of EBSD measure, Cube
It is orientated { 001 }<1 0 0>Area occupation ratio be 5%~50%, and I { 200 }/I0{ 200 } >=2.5, wherein, I { 200 } is to come from
X-ray diffraction intensity, the I in { 200 } face of the copper alloy surface0{ 200 } it is the X from fine copper standard powder { 200 } face
Ray diffraction intensity.
2. copper alloy plate as claimed in claim 1, it is characterised in that 0.2% yield strength is more than 850MPa, and bending adds
Work is less than 1, and the bendability is that bending flawless and that bending gauffer is small can be carried out in 90 ° of W bend tests
The unit of value r/t, the minimum bending radius r and thickness of slab t obtained by the minimum bending radius r divided by thickness of slab t of processing are mm.
3. copper alloy plate as claimed in claim 1, it is characterised in that the copper alloy further adds up to and contains 0.005 matter
Measure being selected from by least one of Sn, Zn, Ag, Mn, B, P, Mg, Cr, Zr, Si and Hf group formed of the mass % of %~1.0.
4. copper alloy plate as claimed in claim 3, it is characterised in that 0.2% yield strength is more than 850MPa, and bending adds
Work is less than 1, and the bendability is that bending flawless and that bending gauffer is small can be carried out in 90 ° of W bend tests
The unit of value r/t, the minimum bending radius r and thickness of slab t obtained by the minimum bending radius r divided by thickness of slab t of processing are mm.
5. the copper alloy plate as described in any one of Claims 1 to 4, it is characterised in that represent to apply constant stress to sheet material
When it is displacement, using the Young's modulus that stretching test measurement obtains as 90GPa~120GPa, determine what is obtained with bending test
Bending coefficient is 80GPa~110GPa.
6. an Albatra metal part, it is made up of the copper alloy plate described in any one of Claims 1 to 5.
7. a kind of connector, it is made up of the copper alloy plate described in Claims 1 to 5 any one of item.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010195120 | 2010-08-31 | ||
| JPJP2010-195120 | 2010-08-31 | ||
| CN201180040769.0A CN103069026B (en) | 2010-08-31 | 2011-08-29 | Copper alloy plate and manufacture method thereof |
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| CN201180040769.0A Division CN103069026B (en) | 2010-08-31 | 2011-08-29 | Copper alloy plate and manufacture method thereof |
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| CN105671358A CN105671358A (en) | 2016-06-15 |
| CN105671358B true CN105671358B (en) | 2018-01-02 |
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| CN201180040769.0A Expired - Fee Related CN103069026B (en) | 2010-08-31 | 2011-08-29 | Copper alloy plate and manufacture method thereof |
| CN201610130170.0A Active CN105671358B (en) | 2010-08-31 | 2011-08-29 | Copper alloy plate, copper alloy part and connector |
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| CN201180040769.0A Expired - Fee Related CN103069026B (en) | 2010-08-31 | 2011-08-29 | Copper alloy plate and manufacture method thereof |
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| EP (1) | EP2612934A1 (en) |
| JP (1) | JP5261582B2 (en) |
| KR (2) | KR20150143893A (en) |
| CN (2) | CN103069026B (en) |
| TW (1) | TWI447239B (en) |
| WO (1) | WO2012029717A1 (en) |
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| US9002499B2 (en) * | 2012-03-20 | 2015-04-07 | GM Global Technology Operations LLC | Methods for determining a recovery state of a metal alloy |
| JP6246456B2 (en) * | 2012-03-29 | 2017-12-13 | Ｊｘ金属株式会社 | Titanium copper |
| JP5826160B2 (en) * | 2012-04-10 | 2015-12-02 | Jx日鉱日石金属株式会社 | Rolled copper foil, copper-clad laminate, flexible printed wiring board and manufacturing method thereof |
| JP6219070B2 (en) * | 2012-06-15 | 2017-10-25 | 古河電気工業株式会社 | Method for producing copper alloy sheet |
| JP6039868B2 (en) * | 2012-12-27 | 2016-12-07 | 株式会社Ｕａｃｊ製箔 | Method for producing negative electrode current collector for secondary battery |
| EP2830158B1 (en) | 2013-02-23 | 2017-12-27 | Furukawa Electric Co., Ltd. | Terminal, wire connection structure, and method for manufacturing terminal |
| JP6639908B2 (en) * | 2013-09-06 | 2020-02-05 | 古河電気工業株式会社 | Copper alloy wire and method of manufacturing the same |
| JP6170386B2 (en) * | 2013-09-10 | 2017-07-26 | 株式会社アマダホールディングス | Method of bending metal plate material and laser processing apparatus used in the bending method |
| CN106103756B (en) * | 2014-03-25 | 2018-10-23 | 古河电气工业株式会社 | The manufacturing method of copper alloy plate, connector and copper alloy plate |
| EP3128036B1 (en) * | 2014-03-31 | 2020-07-01 | Furukawa Electric Co. Ltd. | Rolled copper foil, method for producing rolled copper foil, flexible flat cable, and method for producing flexible flat cable |
| JP2016211077A (en) * | 2016-07-26 | 2016-12-15 | Ｊｘ金属株式会社 | Titanium copper |
| JP6345290B1 (en) * | 2017-03-22 | 2018-06-20 | Ｊｘ金属株式会社 | Copper alloy strip with improved dimensional accuracy after press working |
| JP6310131B1 (en) | 2017-09-22 | 2018-04-11 | Ｊｘ金属株式会社 | Titanium copper for electronic parts |
| JP6310130B1 (en) | 2017-09-22 | 2018-04-11 | Ｊｘ金属株式会社 | Titanium copper for electronic parts |
| CN107768474A (en) * | 2017-10-31 | 2018-03-06 | 苏州为能新型材料有限公司 | A kind of manufacture craft of tin-coated copper strip |
| CN112481518A (en) * | 2019-12-26 | 2021-03-12 | 浙江杭机新型合金材料有限公司 | High-strength high-conductivity copper-titanium alloy material and preparation method thereof |
| CN111413212A (en) * | 2020-04-29 | 2020-07-14 | 北京汇磁粉体材料有限公司 | Device and method for testing bending strength of injection molding material |
| 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 |
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- 2011-08-29 EP EP11821733.0A patent/EP2612934A1/en not_active Withdrawn
- 2011-08-29 WO PCT/JP2011/069467 patent/WO2012029717A1/en active Application Filing
- 2011-08-29 CN CN201180040769.0A patent/CN103069026B/en not_active Expired - Fee Related
- 2011-08-29 JP JP2011553222A patent/JP5261582B2/en active Active
- 2011-08-29 KR KR1020157034879A patent/KR20150143893A/en not_active Application Discontinuation
- 2011-08-29 KR KR1020137004567A patent/KR101577877B1/en not_active IP Right Cessation
- 2011-08-29 CN CN201610130170.0A patent/CN105671358B/en active Active
- 2011-08-29 TW TW100131016A patent/TWI447239B/en active
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Also Published As
| Publication number | Publication date |
|---|---|
| JP5261582B2 (en) | 2013-08-14 |
| TW201211281A (en) | 2012-03-16 |
| CN103069026B (en) | 2016-03-23 |
| KR101577877B1 (en) | 2015-12-15 |
| WO2012029717A1 (en) | 2012-03-08 |
| KR20130099009A (en) | 2013-09-05 |
| CN105671358A (en) | 2016-06-15 |
| EP2612934A1 (en) | 2013-07-10 |
| JPWO2012029717A1 (en) | 2013-10-28 |
| KR20150143893A (en) | 2015-12-23 |
| CN103069026A (en) | 2013-04-24 |
| TWI447239B (en) | 2014-08-01 |
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