CN106148753A - Copper alloy - Google Patents
Copper alloy Download PDFInfo
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- CN106148753A CN106148753A CN201610150835.4A CN201610150835A CN106148753A CN 106148753 A CN106148753 A CN 106148753A CN 201610150835 A CN201610150835 A CN 201610150835A CN 106148753 A CN106148753 A CN 106148753A
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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
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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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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Abstract
Realize display high strength & high electric-conduction and the bendability of excellence and show the copper alloy of the most excellent proof stress relaxation property.This copper alloy in terms of quality % containing Cr:0.15～0.4%, Si:0.01～0.1% and at least one element in Ti and Zr: amount to 0.005～0.15%, surplus is made up of copper and inevitable impurity, and the mean particle diameter utilizing the particle size distribution of the precipitate that low-angle scattering of X-rays method measures is more than 2.0nm and below 7.0nm, and the scope that standardization variance is 30～40% of above-mentioned particle size distribution.
Description
Technical field
The present invention relates to an Albatra metal.Particularly relate to show high strength & high electric-conduction and the bendability of excellence and
The copper alloy of the proof stress relaxation property that display is excellent.
Background technology
In recent years, along with miniaturization and the light-weighted requirement of electronic equipment, answering of the electrical system of electrical and electronic parts
Various material for electrical/electronic components are required thin-walled property, are resistant to complicated shape by hydridization, highly integrated continuous progress
The characteristic of processing.Such as, made in constituting the energized components such as the adapter of electrical and electronic parts, lead frame, relay, switch
Material for electrical/electronic component the sectional area of the material by same load can be made to diminish, relatively because of small-sized, thin-walled property
Sectional area in the material of turn on angle also diminishes.It is therefore desirable to be resistant to when the assembling of electric/electronic device or when working
The high intensity of the stress given, with suppression by the high conductivity being produced as purpose of the Joule heat caused by energising and at electricity
Even if pneumoelectric subassembly is curved processing and does not the most produce the excellent bendability of fracture etc. when manufacturing.
As the above-mentioned copper alloy that improve high strength & high electric-conduction, bendability, such as in patent documentation 1～3
Propose Cu-Cr-Ti-Si alloy or its manufacture method.
The chromium amount that defines, titanium amount, the copper of silicon amount, chromium, titanium, the alloy of silicon is proposed in patent documentation 1, and, as
The manufacturing condition of this alloy, it is provided that after casting, alloy at a temperature of 850 DEG C～950 DEG C with 1 hour～24 hours
Homogenize, and hot rolling more than 1 time at a temperature of 600 DEG C～830 DEG C, cold with 10 DEG C/min～2000 DEG C/min
But speed is cooled to room temperature, carry out afterwards cold rolling, anneal, be tempered.
In patent documentation 2, propose an Albatra metal, which specify Cr amount, Ti amount, Si amount, above-mentioned Cr and above-mentioned Ti
The mass ratio of mass ratio, above-mentioned Cr and above-mentioned Si, and for precipitate, Cr, Ti contained in above-mentioned copper alloy and
In the total amount of Si more than 70% precipitation, above-mentioned copper alloy width cross section away from above-mentioned copper alloy surface thickness side
More than the diameter of equivalent circle 300nm that scanning electron microscope is observed is utilized in the region of 25 μ m cross-sectional direction 40 μm
Precipitate be less than 50, and utilize the diameter of equivalent circle that transmission electron microscope observes on the surface of above-mentioned copper alloy
The average equivalent circular diameter of the precipitate less than 300nm is below 15nm.It addition, it is also proposed a kind of copper in patent documentation 3
Alloy, which specify Cr amount, Ti amount, Si amount, above-mentioned Cr and the mass ratio of above-mentioned Ti, the mass ratio of above-mentioned Cr and above-mentioned Si, and
And for precipitate, utilize 500nm × 500nm district that transmission electron microscope is observed on the surface of above-mentioned copper alloy
The precipitate of below the diameter of equivalent circle 5nm in territory is more than 200.
Cu-is proposed as in the copper alloy of the composition different from above-mentioned Cu-Cr-Ti-Si alloy, such as patent documentation 4
Cr-Zr-Si alloy.This Cu alloy contains Zr and Cr, and surplus is made up of Cu and inevitable impurity, and hot strength is 600N/
mm2Above, conductivity is more than 75%IACS, the bending examination to the length direction direction vertical with rolling direction and thickness of slab direction
Test the thickness not producing minimum bending radius R and the copper alloy plate ruptured after sheet carries out 90 ° of W bend tests according to JIS H3110
Degree t than R/t less than 1.0.This Cu alloy also makes above-mentioned high strength & high electric-conduction, bendability improve.
It addition, propose to improve the precipitation hardening type copper alloy foil of intensity and ductility in patent documentation 5.Should
Copper alloy foil is the copper alloy of Cu-Cr-Zr system, and the tissue of the section vertical with rolling direction meets: (1) 600nm × 400nm's
The crystal grain diameter of the parent phase in region is below 50 μm；(2) any 100 analysis containing Cr or Zr existed in above-mentioned zone
Going out in thing, the arithmetic mean of instantaneous value of the diameter that above-mentioned crystal grain diameter is maximum is below 15nm；(3) any 10 in above-mentioned zone
The 900nm of position2Region in, the number of the precipitate of below 15nm is more than 5.
Prior art literature
Patent documentation
Patent documentation 1: No. 2515127 publications of Japanese Patent No.
Patent documentation 2: Japanese Unexamined Patent Publication 2013-173986 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2014-114485 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2012-162776 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2012-92368 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2012-214882 publication
Summary of the invention
The problem that invention is to be solved
But, when copper alloy being made in vehicle environment in the case of spring uses, exist be exposed to higher than room temperature
Temperature and make stress relaxation phenomenon carry out, produce the problems such as spring retentivity reduction.But, at above-mentioned patent documentation 1～3
In, although in view of the intensity of copper alloy, electric conductivity, bendability, but do not study the raising of proof stress relaxation property.
It addition, the most do not study the raising of proof stress relaxation property in above-mentioned patent documentation 4,5.
Try hard to improve proof stress for vehicle-mounted parts of electric etc. as further contemplating on the basis of above-mentioned high intensity etc.
The copper alloy of relaxation property, proposes regulation Cr amount, Ti amount, Si amount, Ni amount, Fe amount and Al amount in patent documentation 6 and does not has
The copper alloy of recrystallized structure.But, in recent years, it is desirable to show higher proof stress relaxation property.
Currently invention addresses situation as above, its object is to realize display high strength & high electric-conduction and excellence
Bendability, and show the copper alloy of the most excellent proof stress relaxation property.
Means for solving the above
Can solve the problem that the copper alloy of the present invention of the problems referred to above has some main idea following: containing Cr in terms of quality %:
0.15～0.4%, Si:0.01～0.1% and at least one element in Ti and Zr: amount to 0.005～0.15%, remaining
Measure by copper and inevitably impurity constitute, and, utilize the putting down of particle size distribution of the precipitate that low-angle scattering of X-rays method measures
All particle diameters are more than 2.0nm and below 7.0nm, and the scope that standardization variance is 30～40% of above-mentioned particle size distribution.
Above-mentioned copper alloy can also be containing more than a kind in following (a)～(c) as other elements.A () is with quality %
Meter, at least one element in Fe, Ni and Co: altogether more than 0% and less than 0.3% (b) is in terms of quality %, Zn: exceed
0% and less than 0.3% (c) in terms of quality %, at least one element in Sn, Mg and Al: altogether more than 0% and 0.3% with
Under
Invention effect
According to the present invention it is possible to provide by the granularity making precipitate more miniaturization and controlling precipitate compared with the past
It is distributed and shows high strength & high electric-conduction and the bendability of excellence and show that the copper of excellent proof stress relaxation property closes
Gold.
Detailed description of the invention
The present inventor etc. are repeated further investigation to solve the problems referred to above.That is, at above-mentioned patent documentation 2～6
Although technology in the amount of thick compound, the average-size of precipitate are controlled, but, in order to make intensity, conduction
Property, bendability and proof stress relaxation property increase than ever, it is believed that need in copper alloy, with Cr's Yu Si
The shape of the precipitate that the forms such as the compound of compound, the compound of Ti Yu Si, the compound of Zr Yu Si, Ti, Zr and Si separate out
State is further studied, and is studied the form of this precipitate in all its bearings.Itself found that: if based on
The particle size distribution of above-mentioned precipitate when utilizing low-angle scattering of X-rays method to measure and make the mean particle diameter of this particle size distribution micro-
Thin and in being in certain limit and the standardization variance of this particle size distribution is in certain limit, then can reach above-mentioned spy
Property.Thus complete the present invention.
First, the form of this precipitate is illustrated.
As noted above, the regulation of the precipitate form of the present invention is based on using the small-angle scattering mensuration that have employed X-ray
The particle size distribution of the precipitate that method measures.Such as, utilize transmission electron micro-for enforcement in above-mentioned patent documentation 3 grade
For the observation of mirror, although average-size can be measured, but due to the finest and dislocation contrast, and chi cannot be measured
Very little distribution.On the other hand, the most as shown in the above, even if using precipitate fine, it is also possible to Accurate Determining granularity is divided
The low-angle scattering of X-rays method of cloth.Hereinafter, low-angle scattering of X-rays method is illustrated.
The small-angle scattering method itself that have employed X-ray is known as investigating the representative of nano level tectonic information very early
Method.If to material X-ray irradiation, then the information of incident X-rays reflection electron density distribution within material, penetrates at incident X
Surrounding's generation scattered x-ray of line.Such as, if there is particle or the uneven region of electron density in material, the most no matter tie
Crystalline substance or noncrystalline etc., X-ray interferes and produces because of the scattering caused by density fluctuation.If this material is the metals such as copper alloy,
When then there is nano level fine particle in copper alloy tissue, observe the scattering from particle.
Such as in Japanese Unexamined Patent Publication 2014-62284 publication, above-mentioned low-angle scattering of X-rays method is for measuring Al-Zn-
The average-size of the precipitate that the intensity in Mg line aluminium alloy impacts, standardization variance.
But, the scattering observed is derived from the scattering of precipitate and the adduction of the scattering coming from dislocation.Such as above-mentioned Japan
JP 2014-62284 publication adds Zn or Mg like that and up to counts % and come from the scattering of precipitate and sufficiently above come from dislocation
Scattering time, it is possible to carry out ignoring the parsing of the scattering from dislocation.But, as the copper alloy of the present invention, even containing
Measure the highest essential component Cr, lack scattering hour that is the fewest to less than 0.4%, i.e. precipitate amount and that come from precipitate at its content,
The scattering coming from dislocation cannot be ignored.
To this end, for the evaluation of precipitate, implement and apply flexibly abnormal scattered small-angle scattering mensuration.Such as at " radiating light "
In vol.19, No.6,419-427 etc., known exception small-angle scattering is as by utilizing the energy near absorption edge to make X-ray
Energy change and the method that only obtains coming from the scattering of precipitate.
Will to the mean particle diameter of the particle size distribution of copper alloy tissue test nano-precipitation, represent this particle size distribution
The standardization variance of range, first, the scattering strength of X-ray that try to achieve copper alloy plate, that utilize low-angle scattering of X-rays method to measure
Curve.The scattering strength curve of X-ray such as the scattering strength i.e. scattering strength of scattered x-ray with the longitudinal axis as X-ray, transverse axis
It is nm for depending on the unit measuring angle 2 θ and wavelength X-1Wave vector q try to achieve.The scattering strength of this X-ray uses
Under than the Cr higher 5985eV of absorption edge energy measure scattering strength with under the 5720eV lower than Cr absorption edge energy
The difference of the scattering strength measured.
The present invention becomes the mean particle diameter of the particle size distribution of the nano-precipitation of object, represents this particle size distribution
The standardization variance of range can be tried to achieve by the scattering strength curve of above-mentioned X-ray.That is, dissipating of the X-ray obtained according to mensuration
Penetrate the intensity mode close to the X-ray scattering strength calculated by the theoretical formula shown in the function of particle diameter and distribution of sizes, profit
It is fitted with non-linear minimum 2 multiplication, thus can be in the hope of particle diameter and standardization variance yields.
The parsing of the particle size distribution of small precipitate is tried to achieve as the scattering strength curve of this kind of X-ray is resolved
Method, parsing software, such as, can use the known analytic method of Schmidt etc., such as I.S.Fedorova and
Method described in P.Schmidt:J.Appl.Cryst.1 1,405,1978.
The copper alloy of the present invention utilizes the averaged particles of the particle size distribution of the precipitate that above-mentioned low-angle scattering of X-rays method measures
In the scope of a diameter of more than 2.0nm and below 7.0nm.The mean particle diameter of the particle size distribution of this precipitate is especially to intensity
Impact is brought with electric conductivity.In order to ensure high intensity, making above-mentioned mean particle diameter is below 7.0nm.Above-mentioned averaged particles is straight
Footpath is preferably below 6.5nm, more preferably below 6.0nm.On the other hand, if above-mentioned mean particle diameter is too small, then cannot fill
Ground is divided to generate precipitate, the easy step-down of conductivity.Therefore, above-mentioned mean particle diameter is more than 2.0nm.Above-mentioned averaged particles is straight
Footpath is preferably more than 3.0nm, more preferably more than 3.5nm.
And then, the standardization variance of the above-mentioned particle size distribution of the copper alloy of the present invention meets 30～40%.Such as following formula (1)
Shown in, this standardization variance is that the range mean particle diameter of particle size distribution has been carried out standardized parameter.Should if using
Standardization variance, then do not interfere with each mean particle diameter of each sample, can compare the range of particle distribution.In following formula
(1) in, σ be standardization variance, n be population, xi be particle diameter,<x>be that the addition of particle diameter is average.
[mathematical formulae 1]
The present inventor etc. find: by by the mean particle diameter of the particle size distribution of above-mentioned precipitate and this precipitation of expression
The value of the standardization variance of the particle size distribution size of thing controls in certain scope, so that intensity, electric conductivity, proof stress are lax
Characteristic and the balancing good of bendability.Precipitate is continuously generated, grows, therefore, if producing precipitation, then standard fully
The value changing variance becomes big.In other words, in the case of the value of standardization variance is too small, exists and will not fully produce precipitation, intensity,
Electric conductivity, the tendency of the easy step-down of proof stress relaxation property.On the other hand, in the case of the value of standardization variance is excessive,
The final operation beyond timeliness generates precipitate, thus it is speculated that there is the compound of various sizes.Therefore, in standardization variance
Be worth excessive in the case of, there is intensity, tendency that bendability easily deteriorates.
Shown in embodiment as be described hereinafter, in order to ensure intensity more than certain level, electric conductivity, proof stress relaxation property and
Bendability, needing the value making this standardization variance is 30～40%.The value of above-mentioned standardization variance be preferably 32～38%,
More preferably 32～36%.
Then, the one-tenth to the copper alloy of the present invention be grouped into carry out as described below.It should be noted that in becoming to be grouped into
% refer to quality %.
(Cr:0.15～0.4%)
Cr is to be separated out by the form with the metal Cr of simple substance or with the compound of Si, Ti, Zr and improve the strong of copper alloy
The element of degree.If Cr amount is less than 0.15%, then precipitate amount is very few, it is difficult to guarantee intensity.If it addition, Cr amount is not enough, then with Cr
The amount of precipitation separated out with the form of the compound of Si, Ti, Zr reduces, and its result makes solid solution Ti, solid solution Zr, solid solution Si increase, leads
Electricity rate reduces.Therefore, Cr amount is more than 0.15%.Cr amount is preferably more than 0.20%, more preferably more than 0.25%.The opposing party
Face, if Cr measures more than 0.4%, then solid solution Cr excess, has undesirable effect bendability.It addition, conductivity also diminishes.Cause
This, Cr amount is less than 0.4%.Cr amount is preferably less than 0.35%.
(Si:0.01～0.1%)
Si is to make the compound with Cr, Ti, Zr separate out and be favorably improved the element of the intensity of copper alloy.If Si amount is less than
0.01%, then precipitate amount is very few, it is difficult to guarantee required intensity.Therefore, Si amount is more than 0.01%.Si amount is preferably
More than 0.015%.On the other hand, if Si measures more than 0.1%, then Si Yu Cr, Ti, Zr easily form thick crystalline substance and go out thing.Its knot
Fruit makes intensity be easily reduced and bendability also brings harmful effect.If it addition, Si amount excess, then solid solution Si also becomes
Many, conductivity also diminishes.Therefore, Si amount is less than 0.1%.Si amount is preferably less than 0.08%, more preferably less than 0.07%.
(at least one element in Ti and Zr: amount to 0.005～0.15%)
Ti and Zr is lax by improving the intensity of copper alloy and proof stress with the form of the compound of Cr, Si to separate out
The element of characteristic.It addition, Ti and Zr is the unit of the effect of the solid solution limit reduction also having and making Cr, Si the precipitation promoting them
Element.In order to give full play to their effect, the total content of Ti and Zr is set to more than 0.005% by the present invention.Ti's and Zr is total
Content is preferably more than 0.02%, more preferably more than 0.030%.On the other hand, if the total content of Ti and Zr is more than 0.15%,
Then the quantitative change of solid solution Ti and solid solution Zr obtains too much, and conductivity is easily reduced.It addition, bendability the most easily deteriorates.Therefore, Ti
And the total content of Zr is less than 0.15%.The total content of Ti and Zr is preferably less than 0.09%, more preferably less than 0.080%.
Ti and Zr can be a kind, it is also possible to and use.It should be noted that above-mentioned total content is single individually containing Ti or Zr time
Content, is total amount when containing 2 kinds.
The present invention meets mentioned component composition, and surplus is copper and inevitable impurity.As inevitable impurity, example
As Mn, Ca, V, Nb, Mo, elements such as w can be enumerated.If this inevitable impurity is many containing quantitative change, then intensity, electric conductivity, bending
Processabilities etc. can reduce, and is therefore preferably less than 0.1%, more preferably less than 0.05% in terms of total amount.
The copper alloy of the present invention can be the copper alloy possibly together with following element.
(at least one element in Fe, Ni and Co: altogether more than 0% and less than 0.3%)
Fe, Ni, Co have the compound made with Si and separate out and improve the intensity of copper alloy and the effect of electric conductivity.For this
For planting effect, the combination in any of Fe, Ni, Co, i.e. Fe-Ni, Fe-Co, Ni-Co all play same effect, is comprising
Also same effect is played when whole Fe, Ni, Co.That is, these elements can be used alone, it is possible to use two or more.For
Effectively playing the effect above, the total content of above-mentioned element is preferably more than 0.01%, more preferably more than 0.015%.Separately
On the one hand, if the total content of above-mentioned element is more than 0.3%, then solid solution capacity becomes too much, and conductivity reduces.If it addition, above-mentioned unit
The total content excess of element, then these elements and Cr, Ti, Zr easily form thick compound, and the value of standardization variance becomes big, right
Intensity, bendability also produce harmful effect.Therefore, the total content of above-mentioned element is preferably less than 0.3%, is more preferably
Less than 0.2%.It should be noted that the total content of above-mentioned element is single content individually containing Fe, Ni, Co time, containing
It it is total amount when having multiple.
(Zn: more than 0% and less than 0.3%)
Zn is to improving Sn plating material, the resistance to thermally strippable of solder and the suppression hot soarfing of the joint for electronic unit from effectively
Element.In order to effectively play this effect, preferably comprise the Zn of more than 0.01%.On the other hand, if Zn amount excess, then conduct electricity
Rate becomes too low, and therefore Zn amount is preferably less than 0.3%.Zn amount more preferably less than 0.1%.
(at least one element in Sn, Mg and Al: altogether more than 0% and less than 0.3%)
Sn, Al, Mg are the elements being improved intensity by solid solution.These elements can be used alone, it is possible to use 2 kinds
Above.In order to effectively play the effect above, the total content preferably making above-mentioned element is more than 0.01%.On the other hand, if on
State the total content excess of element, then conductivity becomes too low, or bendability reduces, and the total content of the most above-mentioned element is excellent
Elect less than 0.3%, more preferably less than 0.1% as.It should be noted that the total content of above-mentioned element individually containing Sn, Mg,
It is single content during Al, containing being total amount time multiple.
Then, the preferably fabricated condition of the copper alloy of the present invention is illustrated.
First, will have adjusted into the copper alloy that is grouped into melt, casting, and the ingot casting of gained heated (include all
Heat treatment) after carry out hot rolling, then carry out cold rolling, carry out Ageing Treatment afterwards, be thus manufactured as the present invention's of soleplate
Copper alloy.
The melting of copper alloy, casting, heat treated afterwards can utilize usual way to carry out.Such as will be adjusted to
After the copper alloy of regulation chemical composition composition melts in electric furnace, continuous casting etc. is utilized to carry out cast copper alloy ingot casting.Afterwards, add
Heat treatment is that ingot casting is heated to about substantially 800～1000 DEG C, and keep as required certain time, such as 10～120 points
Clock.
In the present invention, the reduction ratio of hot rolling is not particularly limited, as long as according to target thickness of slab and cold rolling with rear operation
The relation of reduction ratio determine.It should be noted that hot rolling can divide 1 time or repeatedly carry out.
In the present invention, in order to obtain showing that above-mentioned being organized as purpose of particle size distribution makes the Ageing Treatment of rear operation
The precipitate that middle generation is fine, it is important that improve the solid solution Cr amount in the copper alloy after hot rolling, solid solution Ti amount, solid solution Zr amount.
In order to improve solid solution Cr amount, solid solution Ti amount, solid solution Zr amount, specifically, preferably: (A) make the end temp of hot rolling be 800 DEG C with
On, or (B) implement the solution treatment of more than 800 DEG C after hot rolling.In the case of above-mentioned (A), the end temp of hot rolling is more
It is preferably more than 830 DEG C.In the case of above-mentioned (B), solid solution temperature be more preferably more than 830 DEG C, more preferably
More than 850 DEG C, the upper limit is substantially 1000 DEG C.The solution treatment time can be such as 10 seconds～about 30 minutes.
Room temperature all it is chilled to after being expected to the hot rolling of above-mentioned (A) and after the solution treatment of above-mentioned (B).This be due to: if heat
Rate of cooling after rolling is little, then generate thick precipitate in cooling procedure, even if carrying out Ageing Treatment, and also cannot be fully
Generate fine precipitate, it is impossible to obtain required tissue.In the present invention, what chilling referred to exceed air cooling averagely cools down speed
The cooling that degree is carried out, preferably more than 20 DEG C/sec.The upper limit of above-mentioned average cooling rate is not particularly limited, if considering reality
Operation etc., less than the most substantially 500 DEG C/sec.Chilling means are not particularly limited, such as, water-cooled etc. can be used various known
Cooling way.
Cold rolling condition is not particularly limited, and can use common condition.For example, it is possible in cold rolling rate 80～enter for 99% time
OK.Rolling number of times is also not particularly limited.
Ageing Treatment is carried out after cold rolling.In the present invention, in order to be organized as mesh with obtain showing above-mentioned particle size distribution
And the standardization variance of the particle size distribution of precipitate is controlled regulation scope, it is important that when making the holding of Ageing Treatment
Between change for a long time.If the retention time is too short, then precipitation size, standardization variance become too small, make various deterioration in characteristics.Specifically
For, the arrival temperature carrying out Ageing Treatment is set to 300～550 DEG C, and by the retention time at these 300～550 DEG C
It is set to more than 5 hours.This retention time is preferably more than 6 hours.If it addition, consider productivity ratio etc., above-mentioned retention time upper
It is limited to about 24 hours.Holding at above-mentioned 300～550 DEG C is except keeping in addition at single temperature, if this temperature model
In enclosing, it is also possible to there is rising or falling of the variation of temperature, i.e. temperature.Such as, temperature is made to occur even as continuous annealing
Continue or periodically change.
Until carrying out average heating speed the indefinite of the arrival temperature of above-mentioned Ageing Treatment.It addition, at above-mentioned timeliness
Average cooling rate after reason also indefinite.Can enumerate: by such as water-cooled or let cool and be cooled to room temperature after above-mentioned Ageing Treatment.
Embodiment
Hereinafter, enumerating embodiment and further illustrate the present invention, the present invention is surely not by following embodiment
Limiting, also it is of course possible to the scope addressing purport described later on can meeting is implemented after being changed, these are all contained in this
In the technical scope of invention.
In kryptol furnace, under Linesless charcoal is coating, copper alloy is melted in an atmosphere, be cast as cast iron imperial decree mould (book
Mold), the ingot casting with the thick 45mm of the chemical composition that table 1 below is recorded is obtained.
After the surface of this ingot casting is carried out flush cut, it is heated, after arriving 1000 DEG C, carry out preserving 30 minutes～2 little
Time equal heat treatment, afterwards, be hot-rolled down to thickness and reach 20mm, with the hot rolling end temp shown in table 2 below: 700～850 DEG C of knots
Bundle hot rolling, with average cooling rate: 20 DEG C/sec carry out water-cooled.In the present embodiment, in order to make above-mentioned hot rolling end temp occur
Change, the air cooling the above-mentioned laggard row of equal heat treatment 5～2 minutes processes, the beginning temperature of change hot rolling.After hot rolling, to portion
Point sample implement the solution treatment of 900 DEG C × 5 minutes, carry out water-cooled, be i.e. chilled to room temperature.
The surface of hot rolled plate is carried out flush cut, removes oxide scale film, so that after thickness is 18mm, carrying out cold rolling,
Obtain the copper alloy plate that thickness is 0.5mm.Afterwards, carry out employing 2 stages of the salt bath that average heating speed is about 50 DEG C/sec
Ageing Treatment or employ average heating speed be about 100 DEG C/h batch anneal stove progressive aging process the most only
The Ageing Treatment in 1 stage.The retention time of 300～550 DEG C is shown in table 2 below in the lump.The No.2 of table 2 below, 6,7,10
And above-mentioned " retention times of 300～550 DEG C " of 11 include time of being warming up to 450 DEG C of needs from 300 DEG C: 1.5 hours.
The copper alloy plate so obtained is used as test film, as shown in following, carries out utilizing the survey of low-angle scattering of X-rays method
Calmly, hot strength and the lax spy of the mensuration of 0.2% yield strength, the evaluation of electric conductivity, the evaluation of bendability and proof stress
The evaluation of property.
(utilizing the mensuration of low-angle scattering of X-rays method)
Low-angle scattering of X-rays measures and the most jointly uses " BL08B2 " of " Spring-8 " and use
The X-ray of the energy of 5720keV and 5985keV is measured, and determines the scattering strength curve of X-ray.Assay device is: right
Test film surface vertically incident X-rays, uses detector to (little with the minute angle of less than 5 degree relative to incident X-rays
Angle) device that is measured of the X-ray that rearward scatters from above-mentioned test film.As measuring sample, use by machinery
Sample after grinding copper alloy plate thin slice chemical conversion about 30 μm.
Use be provided with the known analytic method such as above-mentioned Schmidt, as Co., Ltd. of science manufacture resolving software
Particle diameter hole resolve software " NANO-Solver, Ver.3.5 " so that measure X-ray scattering strength with utilize parsing soft
The mode that the value of the X-ray scattering strength that part calculates is close, utilizes non-linear minimum 2 multiplication scattering strength to this X-ray
Curve is fitted, and thus obtains mean particle diameter and the standardization variance of the particle size distribution of precipitate.It should be noted that
Postulated particle, in the most spherical, use theoretical formula to calculate scattering strength, fits to experiment value, try to achieve above-mentioned averaged particles straight
Footpath.
(hot strength and the mensuration of 0.2% yield strength)
Cut abreast with the rolling direction of copper alloy plate, make the test film of No. 5 sizes of JIS, utilize 5882 types
INSTRON company universal testing machine, is under conditions of 10.0mm/min, GL are 50mm in room temperature, test speed, measures stretching
Intensity and 0.2% yield strength.In the present invention, the situation that 0.2% yield strength is more than 500MPa is evaluated as high intensity.
(evaluation of electric conductivity)
About electric conductivity, by milling drum, copper alloy plate is processed into the test film of the strip of wide 10mm × long 300mm, profit
Measure the resistance of this test film with Double-bridge type resistance measurement device, utilize averga cross section area method to calculate leading in terms of unit %IACS
Electricity rate.In the present invention, the situation that conductivity is more than 80%IACS is evaluated as high conductivity.
(evaluation of bendability)
Bend test is carried out according to Shen Tong association of Japan technical standard.Use and cut into wide 10mm × length from copper alloy plate
The test film of 30mm carries out W bend test.About W bend test, while carry out W bending machining, lateral dominance is with the optical microphotograph of 10 times
Sem observation rupturing with or without bending section.And, obtain the thickness of slab t not producing minimum bending radius R and the copper alloy plate ruptured:
The ratio i.e. R/t of 0.5mm.Situation little for this R/t represents excellent in bending workability.In the present invention, it is the feelings of less than 1.0 by R/t
It is good that condition is evaluated as bendability, is denoted as " OK " in table 3.On the other hand, the R/t situation more than 1.0 is evaluated as bending
Processability is bad, is labeled as " NG " in table 3.
(evaluation of proof stress relaxation property)
Utilize cantilevered fashion to measure stress relaxation rate, thus have rated proof stress relaxation property.Details is as follows.
First, as the sheet material measured, so that length direction becomes the parallel direction (L.D.) of the rolling direction of copper alloy plate and hangs down
Nogata is to the mode of (T.D.), the strip test film of cutting width 10mm × long 60mm.Rigid body testing stand is fixed in its one end,
Distance fixing end certain distance is (following, sometimes referred to as across (span) length.) position to test film give 10mm flexure,
And according to test film each length direction to fixing end load be equivalent to 0.2% yield strength 80% surface stress.Horizontal
Span length's degree utilizes the " based on copper and copper alloy thin plate bar curved of regulation in Japan's Shen Tong association technical standard JCBA-T309:2004
Bent stress relaxation test method " calculate.One end is being fixed on rigid body testing stand and is isolating across length away from fixing end
Under the state that the position of degree gives flexure, each test film is kept 24 hours with 180 DEG C in an oven, is drawn off afterwards, survey
Surely remove permanent strain δ during deflection d:10mm, utilize following formula (2) to measure stress relaxation rate RS.In following formula (2), RS
Represent stress relaxation rate (%), δ represent permanent strain (-), d represent deflection.In this experiment, deflection d is 10mm.At this
In invention, it is qualified the situation that stress relaxation rate RS is less than 15.0% to be evaluated as.
RS=(δ/d) × 100... (2)
Their result is shown in Table 3.
[table 1]
※ surplus is copper and inevitable impurity
[table 2]
[table 3]
It is known as below content by table 1～table 3.No.1,5,8～14 meet the one-tenth of regulation in the present invention and are grouped into and in institute
Manufacture under conditions of recommendation and make the form of precipitate meet regulation, therefore show the bending of high strength & high electric-conduction and excellence
Processability, and show the most excellent proof stress relaxation property.
On the other hand, No.2～4,6,7,15～18 be unsatisfactory in the present invention regulation at least any one, therefore intensity, lead
Electrically, at least any one in bendability, proof stress relaxation property is deteriorated.Shown in details is the most following.
No.2 by be not the example that manufactures under conditions of recommendation, the end temp of hot rolling is low, and is also not carried out solid
Molten process.It addition, the retention time in Ageing Treatment 300～550 DEG C is the shortest.Therefore, the mark of the particle size distribution of precipitate
The value of standardization variance becomes big.Its result is electric conductivity and bendability deterioration.It addition, the No.1 phase identical with chemical composition
Ratio, intensity relative reduction, proof stress relaxation property is deteriorated relatively.
No.3 by be not the example that manufactures under conditions of recommendation, during holding at 300～550 DEG C in Ageing Treatment
Between short.Furthermore, it is believed that: the lower limit 300 DEG C recommended in the temperature of the Ageing Treatment as little as present invention, generate analysis the most fully
Going out thing, the mean particle diameter of the particle size distribution of precipitate and the value of standardization variance are below in the present invention scope of regulation.
Its result is that intensity, electric conductivity, bendability, proof stress relaxation property all deteriorate.
No.4 by be not the example that manufactures under conditions of recommendation, during holding at 300～550 DEG C in Ageing Treatment
Between short.Therefore, precipitate coarsening, the mean particle diameter of the particle size distribution of precipitate becomes big.Its result is that intensity reduces.
No.6 by be not the example that manufactures under conditions of recommendation, the end temp of hot rolling is low, and is also not carried out solid
Molten process.Therefore, the mean particle diameter of the particle size distribution of precipitate and the value of standardization variance become big.Its result be intensity and
Proof stress relaxation property deteriorates.
No.7 by be not the example that manufactures under conditions of recommendation, during holding at 300～550 DEG C in Ageing Treatment
Between short.Therefore, the value of the standardization variance of the particle size distribution of precipitate diminishes.Its result is intensity, electric conductivity and proof stress pine
Relaxation deterioration in characteristics.
In No.15, due to Cr amount excess, therefore bendability reduces.It addition, conductivity also diminishes.
In No.16, due to Ti amount excess, the therefore notable step-down of conductivity, and bendability deteriorates.
In No.17, owing to the total content of Ti Yu Zr is not enough, therefore intensity is low, and proof stress relaxation property also deteriorates.
In No.18, due to Si amount excess, therefore intensity reduces, and conductivity is low, and bendability also reduces.
No.19 and 20 is the example of the scope recommended in the amount deviation present invention of the element arbitrarily added.Wherein,
In No.19, due to Fe amount excess, therefore intensity reduces, and conductivity is low, and bendability also reduces.In No.20, owing to Sn measures
Excess, therefore conductivity is low, and bendability also reduces.
Claims (4)
1. an Albatra metal, it is characterised in that contain in terms of quality %
Cr:0.15～0.4%,
Si:0.01～0.1% and
At least one element in Ti and Zr: amount to 0.005～0.15%,
Surplus is made up of copper and inevitable impurity,
Further, utilize the mean particle diameter of particle size distribution of the precipitate that low-angle scattering of X-rays method measures for more than 2.0nm and
Below 7.0nm, and the scope that standardization variance is 30～40% of described particle size distribution.
Copper alloy the most according to claim 1, possibly together with being selected from more than 0% and less than 0.3% altogether in terms of quality %
At least one element in Fe, Ni and Co, as other elements.
Copper alloy the most according to claim 1 and 2, possibly together with Zn in terms of quality %: more than 0% and less than 0.3% as
Other elements.
4. according to the copper alloy according to any one of claims 1 to 3, possibly together with altogether more than 0% and 0.3% in terms of quality %
The following at least one element in Sn, Mg and Al, as other elements.
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| CN112126815A (en) * | 2020-09-25 | 2020-12-25 | 宁波博威合金板带有限公司 | Copper-chromium alloy strip and preparation method thereof |
| CN114867875A (en) * | 2020-01-14 | 2022-08-05 | 古河电气工业株式会社 | Copper alloy sheet material, method for producing same, and member for electric/electronic component |
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| JP7042979B2 (en) | 2020-03-31 | 2022-03-28 | 古河電気工業株式会社 | Copper alloy plate material and its manufacturing method |
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| JP2016211054A (en) | 2016-12-15 |
| KR101813372B1 (en) | 2017-12-28 |
| KR20160133372A (en) | 2016-11-22 |
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