CN1540012A - Copper alloy and producing method therefor - Google Patents
Copper alloy and producing method therefor Download PDFInfo
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- CN1540012A CN1540012A CNA2003101195051A CN200310119505A CN1540012A CN 1540012 A CN1540012 A CN 1540012A CN A2003101195051 A CNA2003101195051 A CN A2003101195051A CN 200310119505 A CN200310119505 A CN 200310119505A CN 1540012 A CN1540012 A CN 1540012A
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims description 23
- 239000002245 particle Substances 0.000 claims abstract description 116
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 25
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 22
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 22
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims description 36
- 239000006104 solid solution Substances 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 21
- 238000005097 cold rolling Methods 0.000 claims description 19
- 239000010949 copper Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 10
- 239000000956 alloy Substances 0.000 claims description 10
- 238000005096 rolling process Methods 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000000007 visual effect Effects 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052742 iron Inorganic materials 0.000 abstract description 12
- 229910052796 boron Inorganic materials 0.000 abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 8
- 239000010936 titanium Substances 0.000 description 54
- 239000013078 crystal Substances 0.000 description 40
- 230000000052 comparative effect Effects 0.000 description 31
- 229910010165 TiCu Inorganic materials 0.000 description 16
- 238000000137 annealing Methods 0.000 description 14
- 229910052719 titanium Inorganic materials 0.000 description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000003483 aging Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 235000013339 cereals Nutrition 0.000 description 7
- 238000004881 precipitation hardening Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000005098 hot rolling Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 208000034189 Sclerosis Diseases 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011158 quantitative evaluation Methods 0.000 description 3
- 238000005204 segregation Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 235000020985 whole grains Nutrition 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Conductive Materials (AREA)
Abstract
Superior bendability in a copper alloy and further strength improvement ensures characteristics which are sufficiently superior in view of essential qualities of strength of titanium-copper. 2.0 to 4.0 mass % of Ti, 0.01 to 0.50 mass % of one or more than one kind of element from among Fe, Co, Ni, Cr, V, Zr, B, and P as the third element group are contained, and not less than 50% of the total content of these elements is made to exist as second-phase particles.
Description
Technical field
The present invention relates to be used in the copper alloy of connector material etc., particularly provide the manufacturing technology of the copper alloy of having realized good bendability and intensity simultaneously.
Background technology
The copper alloy (following, be called " titanium copper ") that contains titanium is used in connector material etc., it needs the tendency that increases day by day in recent years.Corresponding with this tendency, as to have carried out all and the titanium copper relevant research and development of precipitation-hardening.In copper alloy in the past, in the oriented titanium copper, add the copper alloy (for example, with reference to patent documentation 1) of Ni and Al gained.In addition, also oriented titanium copper adds the copper alloy (for example, with reference to patent documentation 2) of Al and Mg gained.And then the interior copper alloy (for example, with reference to patent documentation 3) that adds Sn, Ni and Co gained of also oriented titanium copper.Proposed to add the technology (for example, with reference to patent documentation 4) of Cr, Zr, Ni and Fe in recent years to titanium copper.In addition, also put down in writing the technology relevant (for example, with reference to patent documentation 5) with the granular of crystal grain.And then proposed to add the technology (for example, with reference to patent documentation 6) of Zn, Cr, Zr, Fe, Ni, Sn, In, P and Si to titanium copper.
[patent documentation 1]
The spy opens clear 50-53228 communique (the 1st, 2 page)
[patent documentation 2]
The spy opens clear 50-110927 communique (the 1st, 2 page)
[patent documentation 3]
The spy opens clear 61-223147 communique (1-3 page or leaf)
[patent documentation 4]
Te Kaiping 6-248375 communique (2-8 page or leaf)
[patent documentation 5]
Te Kaiping 2001-303158 communique (2-4 page or leaf)
[patent documentation 6]
Special hope 2002-31219 communique
Titanium copper forms supersaturated solid solution by solution treatment, when this state is implemented low temperature aging, develops into modulation structure, the interim remarkable sclerosis when this developmental stage a certain of metastable phase.When crossing development, it just becomes so-called overaging state, the TiCu that finally separates out stable phase
3, when this increases mutually, can produce softening on the contrary.In this a series of ag(e)ing process, represent that high-intensity modulation structure is the variation that is caused by unsettled supersaturated solid solution, can not obtain TiCu from stable phase
3Arrive the variation of the modulation structure of metastable phase.On the other hand, under the inadequate situation of solution treatment, the titanium that finishes of solid solution is not as TiCu
3The state of separating out remains in the parent phase down.Therefore be necessary in the solution treatment of its preceding operation, to make TiCu in order to reach the sclerosis under the timeliness to greatest extent
3In other words, titanium is solid-solubilized in the parent phase fully the phase completely dissolve, therefore, is necessary to be heated to the temperature that the solid solution limit that makes titanium surpasses the titanium amount.For example, contain at copper under the situation of 3% titanium, make the complete solid solution of titanium, just the temperature that must be heated to more than 800 ℃ is carried out solution treatment.In addition, titanium copper is identical with other metallic substance, can improve yield strength by granular crystal grain in annealing operation.Under the situation of making titanium copper, the recrystallization annealing operation of common final manufacturing process is equivalent to solution treatment, and the granular that how to realize crystal grain in this solution treatment is to improve the key of yield strength.
,, improve, must under the temperature lower, carry out solution treatment than it for the granular by crystal grain realizes yield strength because crystal grain is easy to thickization in the high-temperature area that makes the complete solid solution of titanium like that in the past.For example, contain in the alloy of 3% titanium, at copper because under aforementioned 800 ℃ condition crystal grain not granular, make the crystal grain granular by carrying out solution treatment at 750～775 ℃.Therefore, under prior art, make the crystal grain granular of titanium copper can cause the solid solution of titanium insufficient, the TiCu that separates out stable phase
3As previously mentioned, at this TiCu that separates out constantly in the grain boundary
3Not only the sclerosis under the timeliness of back operation there is not help, and the shortcoming that bendability is worsened.In addition, in titanium copper, adding the 3rd element (Fe, Co, Ni, Cr, V, Zr, B and P), purpose is to contain in the prior art of the precipitation-hardening of separating out gained of the 2nd phase of these compositions, when guaranteeing fully to obtain the addition of precipitation-hardening, the shortcoming of the formation that hinders the modulation structure is arranged.In addition because for the solid solution condition of the precipitation-hardening that reaches these elements to greatest extent and timeliness condition with in order to produce deviation between the solid solution condition that reaches the original modulation structure of titanium copper to greatest extent and the timeliness condition, so can not fully take into account the development that the modulation of the precipitation-hardening of the 3rd element and titanium copper is constructed.Like this, in the prior art, though can obtain the intensity that the good strength characteristics of titanium copper is difficult to obtain positive α.
The present invention proposes in view of the above problems, purpose is to suppress TiCu
3Separate out and when realizing good bendability, respect the mechanism for intensifying of titanium copper essence, under the condition of fully guaranteeing its good characteristic, seek further intensity and improve.
Summary of the invention
Copper alloy of the present invention is characterised in that: the Ti that contains 2.0～4.0 quality %, as the 3rd groups of elements, contain more than one elements among Fe, Co, Ni, Cr, V, Zr, B and the P of 0.01～0.5 quality %, the existing as the 2nd phase particle more than 50% of the total amount of the 3rd groups of elements.
In the present invention, making the amount of Ti is 2.0～4.0 quality %.Under the situation of amount of Ti, because can not obtain the mechanism for intensifying of the formation gained of the original modulation structure of titanium copper fully, so can not obtain the superior strength of titanium copper less than 2.0 quality %.This is external to surpass under the situation of 4.0 quality %, TiCu
3Be easy to separate out, intensity variation and bendability worsen.In the present invention, the amount by making Ti is suitableization as described above, and can realize good intensity and bendability together.In addition, take into account above-mentioned intensity and bendability with high level more, the amount of then wishing Ti is 2.5～3.5 quality %.
In addition, in the present invention,, suppress TiCu in order in solution treatment, to become sufficient sosoloid
3Promotion of separating out and crystal grain-growth, define the composition of the element (the 3rd groups of elements) that constitutes the 2nd phase particle.Here, so-called the 2nd phase particle is meant that with Cu and Ti be principal constituent, contains integrant X (Fe specifically, Co, Ni, Cr, V, Zr, B, the Cu-Ti-X class particle that generates under situation P) of the 3rd groups of elements.This Cu-Ti-X class particle has been implemented in solution treatment or before the solution treatment also can form under the annealed situation, helps to suppress the crystal grain-growth behind the recrystallize.In addition, this Cu-Ti-X class particle is because thermally-stabilised, and after solution treatment, even implement cold rolling timeliness in the remaining operation before becoming goods, its form also changes hardly.At Fe, Co, Ni, Cr, V, Zr is under the situation of total amount less than 0.01 quality % of B and P, because do not separate out the 2nd phase particle of abundant amount, so the effect of the growth of inhibition crystal grain is little when solution treatment.In addition, at Fe, Co, Ni, Cr, V, Zr, the total amount of B and P surpass under the situation of 0.50 quality %, because the 2nd phase particle is easy to thickization, so bendability worsens.Suitableization of the addition by seeking above-mentioned the 3rd groups of elements can access good especially bendability in the present invention.
, even the amount of above-mentioned the 3rd groups of elements is fit to because if the 3rd groups of elements is not separated out as the 2nd phase particle, the effect that then suppresses crystal grain-growth is little, thus when solution treatment thickization of crystal grain, can not realize the raising of intensity.This external the 3rd groups of elements solid solution is under the state of parent phase, and the formation for the modulation structure when carrying out ageing treatment produces disorder, and hardening capacity reduces.So, be necessary to make Fe, Co, Ni, Cr, V, Zr, the amount of B and P half exists as the 2nd phase particle at least.In the present invention, the existing as the 2nd phase particle more than 50% of the amount by making the 3rd groups of elements, sought suitableization to the amount of the 2nd phase particle of the 3rd groups of elements, can side by side realize the good bendability and the raising of intensity with high level.
Other copper alloy of the present invention in addition is characterised in that: contain the Ti of 2.0～4.0 quality %, as the 3rd groups of elements, contain the Fe of 0.01～0.5 quality %, Co, Ni, Cr, V, Zr, more than one elements among B and the P, and then by the section microscopic examination to area be 0.01 μ m
2In the 2nd above phase particle, the containing ratio of the 3rd groups of elements in the 2nd phase particle is that the ratio of number of the 2nd phase particle more than 10 times of the containing ratio of the 3rd groups of elements in the alloy is more than 70% of the 2nd phase particle integral body.
Copper alloy of the present invention and above-mentioned copper alloy be suitableization of the amount by seeking Ti similarly, suitableization of the amount of the 3rd groups of elements, and can side by side realize the good bendability and the raising of intensity., in the present invention, as mentioned above, be necessary to seek suitableization of the 3rd groups of elements to the amount of the 2nd phase particle.In the present invention, in that observed area is 0.01 μ m by the section microscope
2In the 2nd above phase particle, the ratio of number of the 2nd phase particle more than 10 times that by the containing ratio that makes the 3rd groups of elements in the 2nd phase particle is the containing ratio of the 3rd groups of elements in the alloy is more than 70% of the 2nd phase particle integral body, seeks suitableization of the 3rd groups of elements to the amount of the 2nd phase particle.Therefore, even in copper alloy of the present invention, can side by side realize the good bendability and the raising of intensity with high level.
Copper alloy of the present invention is characterised in that: contains the Ti of 2.0～4.0 quality %,, contains the Fe of 0.01～0.5 quality % as the 3rd groups of elements, and Co, Ni, Cr, V, Zr, more than one elements among B and the P, observed area is 0.01 μ m by the section microscope
2The area occupation ratio A of the 2nd above phase particle
fBe below 1.0%.
In the present invention, making the amount of Ti is 2.0～4.0 quality %.Under the situation of amount of Ti, can not fully obtain the formation gained mechanism for intensifying of the original modulation structure of titanium copper, thereby can not obtain the good intensity of titanium copper less than 2.0 quality %.In addition, surpassing under the situation of 4.0 quality % TiCu
3Be easy to separate out, bendability is worsened.In the present invention, the amount by making Ti is suitableization as described above, and can realize good bendability and intensity jointly.In addition, in order to take into account above-mentioned bendability and intensity, wish that making the amount of Ti is 2.5～3.5 quality % with higher level.
Though the present invention adds the 3rd element in order to form the 2nd phase particle, it is purpose that the 2nd phase particle does not resemble the prior art with the precipitation-hardening, but forms with the purpose of the growth that suppresses crystal grain.Thus, the 3rd groups of elements given to this invention is not the high particle of precipitation-hardening, but from having carried out repeatedly strict screening the material of experiment back gained in the element that forms in order to seek the grain that makes the growth that suppresses crystal grain effectively.Here, so-called the 2nd phase particle is meant that with Cu and Ni be principal constituent, contains integrant X (Fe specifically, Co, Ni, Cr, V, Zr, B, the Cu-Ti-X class particle that generates under situation P) of the 3rd groups of elements.Even this Cu-Ti-X class particle has been implemented in solution treatment or before the solution treatment also can form under the annealed situation, help to suppress the crystal grain-growth behind the recrystallize.In addition, because thermally-stabilised, after solution treatment, even implement cold rolling timeliness in the remaining operation before becoming goods, its form also changes hardly by formed this Cu-Ti-X class particle of the 3rd groups of elements of the present invention.At Fe, Co, Ni, Cr, V, Zr under the situation of total amount less than 0.01 quality % of B and P, because do not separate out the 2nd phase particle of abundant amount, so the effect of the growth of inhibition crystal grain is little when solution treatment, can not realize good bendability.In addition, surpass under the situation of 0.50 quality % at the total amount of Fe etc., the 2nd phase particle is easy to thickization in solution treatment, has produced the side effect that bendability is worsened.Suitableization of the addition by seeking above-mentioned the 3rd groups of elements can access good especially bendability in the present invention.
, even the amount of above-mentioned the 3rd groups of elements is fit to, the 2nd phase particle was excessively separated out when overaging was handled, and bendability worsens, so be necessary to limit for the amount of separating out of the 2nd phase particle.In the present invention, make that observed area is 0.01 μ m by the section microscope
2The area occupation ratio A of the 2nd above phase particle
fBe below 1.0%.Here, so-called above-mentioned area occupation ratio A
fBe meant the ratio of total area of the 2nd phase particle of per unit area, in particular, be meant aggregate value shared ratio in the area of the mensuration visual field of titanium copper of area of the 2nd phase particle of object.This area occupation ratio A
fIn fact can measure by picture processing by observation test portion sections such as SEM.At this area occupation ratio A
fUnder 1.0% the situation of surpassing, the 2nd phase particle becomes the state of excessively separating out, and bendability is worsened.In the present invention, by seeking above-mentioned area occupation ratio A
fSuitableization and can access good especially bendability.
As shown above, according to the present invention, when limiting the amount of Ti, the amount by limiting the 3rd groups of elements and the area occupation ratio A of the 2nd phase particle
fComposition, side by side realize the good bendability and the copper alloy of intensity and can provide.
In addition, copper alloy of the present invention is the copper base alloy that contains the Ti of 2.0～4.0 quality %, it is characterized in that:, contain the Fe of 0.01～0.5 quality %, Co as the 3rd groups of elements, Ni, Cr, V, Zr, more than one elements among B and the P are about observed area is 0.01 μ m by the section microscope
2The 2nd above phase particle, defined impartial dispersity E is below 0.8 by following formula.
Di: distance from i the 2nd phase particle to the 2nd nearest phase particle
Ao: measure visual field area
N
A: the number of the 2nd phase particle of in measuring visual field area, being confirmed
The prerequisite of copper alloy of the present invention is: suitableization of the amount by seeking Ti similarly with above-mentioned copper alloy, and suitableization of the amount of the 3rd groups of elements, and can side by side realize the good bendability and the raising of intensity.,,, then can not suppress the crystal grain-growth in the recrystallization annealing effectively, can not realize good bendability if the uneven quality of the 2nd phase particle that forms is disperseed thus even the amount of above-mentioned the 3rd groups of elements is fit to.In addition, if the uneven quality of the 2nd phase particle is disperseed, then tissue is easy to become stuff and other stuff.When the material that tissue is become stuff and other stuff was implemented the plastic working of flexural deformation or stretching etc., in-house deflection was inhomogeneous, produces difference because of the position is different.Specifically, the part that big more the 2nd phase particle density of crystal grain is more little is easily deformable more, is out of shape in next being difficult to of opposite situation.Promptly; even processing in large quantities; the deflection of part concentrates on easily deformable position; generation is chapped and is spread therefrom; so become big crystal grain mixes the mixed grain that exists with little crystal grain tissue; even this tissue average crystal grain diameter is little, but compare bendability with the tissue of the whole grain of same particle size and intensity is poor.In the present invention, making by the viewed area of section microscope is 0.01 μ m
2The impartial dispersity E that the 2nd above phase particle is relevant is below 0.8.The value of this equalization dispersity E is disperseed more equably near 0 expression the 2nd phase particle more, and this value is big more on the contrary represents that more this is dispersed with deviation.So-called here impartial dispersity E is the brand-new statistical value that present inventors find.Up to the present, the influence of bringing to the character of the distribution of crystal grain or the machinery example that carries out quantitative evaluation not, the also example that isotropism self of the distribution of the 2nd phase particle is not carried out quantitative evaluation to the distribution of the 2nd phase particle.Present inventors are in the process of the crystal structure of investigating all test materialss and mechanical properties, the distribution situation that is conceived to the 2nd phase particle especially continues to observe carefully and notices: even the sum of the 2nd phase particle is identical with area occupation ratio, if the distribution situation difference, then the shape of tissue or machinery also dissimilates.And then the relation of the distributional pattern of the 2nd phase particle and the character of tissue or machinery carried out detailed research and found from various angles: the 2nd approaching more dispersive equably of particle state mutually, crystal grain is more whole grain, and bendability is also good and obtain the tendency of higher yield strength value.So, whether can quantitative evaluation and the result that studies for the isotropism of the distribution of particle, the statistical value of finding out its validity is impartial dispersity E, data can be understood by experiment: surpass under 0.8 the situation in this value, the distribution of the 2nd phase particle has suitable deviation, can not realize good bendability and intensity.Can access good especially bendability and intensity by suitableization of seeking above-mentioned impartial dispersity E in the present invention.
And then, the manufacture method of copper alloy of the present invention is the method that is used for making suitably above-mentioned copper alloy, it is characterized in that: have: at the Fe that in copper, has added 0.01～0.5 quality %, Co, Ni, Cr, V, Zr is behind more than one elements among B and the P, add the Ti of 2.0～4.0 quality %, make the operation of ingot; In ingot being heated to the solution treatment that arrives temperature T ℃, be heated to the heat-up rate more than 20 ℃/second and surpass 600 ℃ temperature, make it to become the solution treatment operation of supersaturated solid solution afterwards more than 10 seconds T-100～T ℃ temperature province heating; Implement cold rolling cold rolling process from the state of super saturated solid solution with 5～50% degree of finish; The pressure rolling material is implemented heat treated ageing treatment process down at 350～450 ℃.
According to the manufacture method of copper alloy of the present invention, suitableization of the addition by seeking Ti, suitableization of the addition of the 3rd groups of elements can side by side realize the good bendability and the raising of intensity.
, as mentioned above, even realized suitableization of the addition of suitableization of addition of Ti and the 3rd groups of elements, if do not reach suitableization of the 3rd groups of elements to the amount of the 2nd phase particle, then bendability that can not obtain expecting and intensity.Theory according to the Zener (Zener) of the relation of the growth of explanation the 2nd phase particle and recrystallize grain, the fine equably dispersion of the 2nd phase particle, the effect that then suppresses crystal grain-growth is big more, for example, open in the clear 58-220139 communique the spy, put down in writing based on this Zener theory, making the 2nd phase particle before the recrystallization annealing operation is the technology of fine dispersive state.Relative with it, present inventors recognize: not before recrystallization annealing, and in the initial stage of the solution treatment that is equivalent to the recrystallization annealing operation just, by making the fine dispersion of the 2nd phase particle, the complete solid solution of titanium makes the abundant granular of crystal grain so that then can take into account bendability and intensity with high level.Specifically, by seeking suitableization of the heat-up rate under the solution treatment, and obtain above-mentioned effect, thereby finish the present invention.That is, in the present invention, realize by be heated to the temperature that surpasses 600 ℃ with the heat-up rate more than 20 ℃/second.This heat-up rate less than 20 ℃/second situation under, can not suppress TiCu
3Separating out of phase, so bendability worsens.In copper alloy of the present invention,, can side by side realize the good bendability and the raising of intensity with high level by seeking suitableization of above-mentioned heat-up rate.
Embodiment
Below, according to its manufacturing process copper alloy of the present invention is described successively.In addition, the manufacture method of operation formation shown below is represented a Production Example of copper alloy of the present invention.
Ingot manufacturing process
In the Cu of specified amount, add in (Fe, Co, Ni, Cr, V, Zr, B and P) with more than one 0.01～0.5 quality % as the 3rd groups of elements, fully keeping the back to add the Ti of 2.0～4.0 quality %.At this moment, though the hold-time with the kind of raw material and quantity and difference was preferably more than 1 hour.For the 3rd groups of elements is worked effectively as the 2nd phase particle, in this ingot manufacturing process, the 3rd groups of elements is dissolved fully not have residual.Therefore after adding the 3rd groups of elements, need to keep fully.In addition, because Ti is easy to be dissolved among the Cu, can after the interpolation of the 3rd groups of elements, add again.
After this ingot manufacturing process, preferably at the homogenizing anneal that carries out more than 950 ℃ more than 10 hours.Eliminate segregation, in solution treatment described later, make the fine and dispersion equably of separating out of the 2nd phase particle, and finally can prevent to mix grain effectively.That is, if carry out this homogenizing anneal fully, can make above-mentioned impartial dispersity E is below 0.8.Therefore, can make the 2nd phase particle, can realize good especially bendability as homogeneous dispersion expectedly.In addition, by carrying out sufficient homogenizing anneal, in solution treatment described later, can prevent that the 2nd phase particle from separating out as thick precipitate.In other words, can make the 2nd phase particle as dispersion imperceptibly expectedly, thereby prevent to mix grain.After this homogenizing anneal, carry out hot rolling, carry out cold rolling repeatedly and annealing, carry out solution treatment.Because annealing midway forms the 2nd phase particle when temperature is low, so carry out under the temperature of the complete solid solution of the 2nd phase particle.If do not add the common titanium copper of the 3rd groups of elements, though being 800 ℃, its temperature gets final product, it is more than 900 ℃ that the titanium copper that has added the 3rd groups of elements preferably makes its temperature.And then in cold rolling before being about to carry out solution treatment, separating out of the 2nd phase particle of the high more solution treatment of its degree of finish is even more and fine.In addition, separate out in order before solution treatment, to make the 2nd fine phase particle, though aforesaid cold rolling after, also can anneal at low temperatures because DeGrain, when considering that the cost of operation due to increasing rises, the good method of can not saying so.If achieve the above object, before solution treatment, carry out under the stress relief annealed situation, wish to carry out in the temperature below 450 ℃ of thickization that does not cause crystal grain.
The solid solution operation
After above-mentioned ingot manufacturing process, carry out solid solution.Here it should be noted that and to be heated to the solid solution limit that the makes Ti temperature bigger (at the addition of Ti is to be 730～840 ℃ in the scope of 2～4 quality % than addition, be 800 ℃ when for example the addition of Ti is 3 quality %), in order in its temperature-rise period, to pass through TiCu apace
3The temperature province that most is easy to separate out is heated at least 600 ℃ with the heat-up rate more than 20 ℃/second.By suitableization of this heat-up rate, can suppress the TiCu of stable phase
3Separate out and when improving bendability, can form the growth of relative recrystallize grain and suppress outstanding effect the 2nd phase particle, promptly be fine and uniform the 2nd phase particle of principal constituent with the 3rd element.In addition, by above-mentioned heat-up rate and suitableization of heat-up time, can make by the observed area of section microscope is 0.01 μ m
2The area occupation ratio A of the 2nd above phase particle
fBe below 1.0%.Thus, the 2nd phase particle can exceedingly not separated out, and can access good especially bendability.
The cold rolling process ageing treatment process
After above-mentioned solid solution operation, carry out cold-rolling treatment and timeliness successively and handle.These processing can corresponding copper alloy purposes under usual method, condition, carry out.For example, using under the situation of copper alloy as connector material, for cold-rolling treatment, hope is cold rolling to the enforcement of the material after the solution treatment 5～50%.In addition, for ageing treatment, wish in 350～450 ℃ the inert atmosphere of Ar gas etc. for example, to implement the ageing treatment about 100～1000 minutes.
[embodiment]
Then, embodiments of the invention are described.
When making copper alloy of the present invention, in view of the Ti with reactive metal adds as the 2nd composition, when molten system, use vacuum dissolving stove, crucible uses the material of graphite system.In addition, in order to prevent the side effect due to the sneaking into of unavoidable impurities element beyond the element given to this invention with preventing trouble before it happens, use purity than higher material (electric copper and pure titanium) as raw material.
At first,, in Cu, add Fe respectively with the composition shown in the table 1 for embodiment 1～10 and comparative example 11～20, Co, Ni, Cr, V, Zr after B and the P, adds the Ti that forms shown in the table 1 respectively.Fully take into account the hold-time after the interpolation so that add element dissolve fully do not have residual after, the gained material is injected mould under Ar atmosphere, make the ingot of about 2kg respectively.
Table 1
(unit of the amount of each element is weight %)
| ??No. | ??Fe | ??Co | ??Ni | ??V | ??Zr | ??Cr | ??P | ??B | ??Ti | Heat-up rate (℃/second) | |
| Embodiment | ??1 | ??0.1 | ??2.4 | ????150 | |||||||
| ??2 | ??0.1 | ??2.3 | ????160 | ||||||||
| ??3 | ??0.2 | ??3.6 | ????30 | ||||||||
| ??4 | ??0.1 | ??0.03 | ??3.1 | ????100 | |||||||
| ??5 | ??0.1 | ??0.04 | ??3.2 | ????80 | |||||||
| ??6 | ??0.2 | ??0.05 | ??2.7 | ????140 | |||||||
| ??7 | ??0.2 | ??3.3 | ????90 | ||||||||
| ??8 | ??0.1 | ??0.2 | ??2.9 | ????130 | |||||||
| ??9 | ??0.2 | ??0.02 | ??3.2 | ????40 | |||||||
| ??10 | ??0.1 | ??0.2 | ??0.02 | ??3.0 | ????120 | ||||||
| Comparative example | ??11 | ??0.1 | ??1.5 | ????110 | |||||||
| ??12 | ??0.1 | ??5.0 | ????120 | ||||||||
| ??13 | ??3.0 | ????130 | |||||||||
| ??14 | ??1.0 | ??3.0 | ????40 | ||||||||
| ??15 | ??0.5 | ??0.5 | ??0.2 | ??3.0 | ????50 | ||||||
| ??16 | ??0.5 | ??0.5 | ??0.3 | ??3.0 | ????150 | ||||||
| ??17 | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.1 | ??0.2 | ??0.2 | ??0.2 | ??2.9 | ????140 | |
| ??18 | ??0.2 | ??0.1 | ??2.8 | ????5 | |||||||
| ??19 | ??0.1 | ??0.3 | ??3.1 | ????7 | |||||||
| ??20 | ??0.3 | ??0.1 | ??3.2 | ????9 |
At coating oxidation inhibitor on the above-mentioned ingot and after dry 24 hours at normal temperatures, implement hot rolling by 950 ℃ * 2 hours heating, obtain the hot-rolled sheet of thickness of slab 10mm.Then on this hot-rolled sheet, be coated with oxidation inhibitor once more, implement to carry out water-cooled after 950 ℃ * 2 hours the heating in order to suppress segregation.Being coated with anti-oxidation materials in addition is to react and the internal oxidation of impurityization with the interpolation elemental composition for the oxygen that prevents the grain boundary oxidation as much as possible and come in from the surface.Each hot-rolled sheet is respectively by mechanical mill and pickling and after the scale removal, be cold-rolled to thickness of slab 0.2mm.Thereafter, insert the annealing furnace that can heat rapidly with having implemented this cold rolling pressure rolling material, be heated to the heat-up rate of table 1 expression and surpass 600 ℃ temperature, finally be heated to the solid solution limit temperature (when the addition of Ti be 3 quality %s is 800 ℃) bigger that makes Ti, keep carrying out water-cooled after 2 minutes than addition.At this moment, measure average crystal grain diameter (GS) by the process of chopping.Thereafter, cold rolling by carrying out after the pickling scale removal, obtain the rolling stock of thickness of slab 0.14mm.This material was heated in inert atmosphere 400 ℃ * 3 hours, make the test film of each embodiment and comparative example.
At coating oxidation inhibitor on the above-mentioned ingot and after dry 24 hours at normal temperatures, implement hot rolling by 980 ℃ * 12 hours heating (homogenizing annealing), obtain the hot-rolled sheet of thickness of slab 10mm.Then on this hot-rolled sheet, be coated with oxidation inhibitor once more, implement to carry out water-cooled after 980 ℃ * 2 hours the heating.This is the measure that is used for further reducing segregation, makes the effective means of dispersive equably of separating out of the 2nd phase particle.Being coated with anti-oxidation materials here is to react and the internal oxidation of impurityization with the interpolation elemental composition for the oxygen that prevents the grain boundary oxidation as much as possible and come in from the surface.In addition because speed of cooling when slow the 2nd phase particle excessively separate out, so water-cooled is used to accelerate the speed of cooling after the solid solution.Hot-rolled sheet after each heating after the scale removal, carries out the cold rolling of appropriateness and annealing by mechanical mill and pickling respectively repeatedly, and it is cold-rolled to thickness of slab 0.2mm., this cold rolling material inserted the annealing furnace that can rapidly heat, be heated to the solid solution limit temperature (when the addition of Ti be 3 quality %s is 800 ℃) bigger that makes Ti for 50 ℃/second, keep carrying out water-cooled after 1 minute than addition with heat-up rate thereafter.At this moment, measure average crystal grain diameter (GS) by the process of chopping.Thereafter, cold rolling by carrying out after the pickling scale removal, obtain the rolling stock of thickness of slab 0.14mm.This material was heated in inert atmosphere 400 ℃ * 3 hours, make the test film of each embodiment and comparative example.The wet type number of quantitative analysis of the test film of these embodiment 1～10 and comparative example 11～20 is as shown in table 2.In addition, the unit of the value shown in the table 2 all is quality %.
In addition, comparative example 14～20 is made test portion under condition described later.
Table 2
| ??No. | ??Ti | ??Fe | ??Co | ??Ni | ???V | ??Zr | ??Cr | ??P | ??B | Cu | |
| Embodiment | ??1 | ??2.3 | ??0.1 | Remainder | |||||||
| ??2 | ??2.4 | ??0.1 | Remainder | ||||||||
| ??3 | ??3.6 | ??0.2 | Remainder | ||||||||
| ??4 | ??3.1 | ??0.1 | ??0.04 | Remainder | |||||||
| ??5 | ??3.2 | ??0.1 | ??0.05 | Remainder | |||||||
| ??6 | ??2.7 | ??0.2 | ??0.03 | Remainder | |||||||
| ??7 | ??3.3 | ???0.2 | Remainder | ||||||||
| ??8 | ??2.9 | ??0.1 | ??0.2 | Remainder | |||||||
| ??9 | ??3.2 | ???0.2 | ??0.03 | Remainder | |||||||
| ??10 | ??3.0 | ??0.1 | ??0.2 | ??0.03 | Remainder | ||||||
| Comparative example | ??11 | ??1.5 | ??0.1 | Remainder | |||||||
| ??12 | ??5.0 | ??0.1 | Remainder | ||||||||
| ??13 | ??3.0 | Remainder | |||||||||
| ??14 | ??3.0 | ??1.1 | Remainder | ||||||||
| ??15 | ??3.0 | ??0.4 | ??0.6 | ??0.2 | Remainder | ||||||
| ??16 | ??3.0 | ??0.5 | ??0.5 | ??0.3 | Remainder | ||||||
| ??17 | ??2.9 | ??0.1 | ??0.3 | ??0.2 | ???0.2 | ??0.1 | ??0.2 | ??0.2 | ??0.2 | Remainder | |
| ??18 | ??2.8 | ??0.1 | ??0.2 | Remainder | |||||||
| ??19 | ??3.1 | ??0.2 | ??0.3 | Remainder | |||||||
| ??20 | ??3.2 | ???0.3 | ??0.1 | Remainder |
Then, for each embodiment and each comparative example, carry out the W pliability test in pressure rolling direction and right angle orientation (bending axis and pressure rolling direction are same directions), when measuring the ratio MBR/t value that does not produce the relative thickness of slab (t) of disruptive minimum bending radius (MBR), measure the validity that 0.2% yield strength is verified embodiment.
In addition, carry out the affirmation that the 2nd phase particle is formed with 2 following methods.At first as the 1st evaluation method, employing is for the material that the test film of certainweight is dissolved gained in phosphoric acid, separate the 2nd phase particle by membrane filter (0.1 μ m mesh), by the composition in the remaining solution is carried out quantitative analysis, calculate the method for the 3rd groups of elements as the ratio of the 2nd phase particle existence.According to this method, making the value of calculating gained for facility is A value (%).The A value is high more, and expression the 3rd groups of elements that the present invention added is high more as the ratio that the 2nd phase particle exists, if the A value is 100%, represents that then the 3rd all groups of elements all exists as the 2nd phase particle.In fact, because the mesh size of strainer is limited, can not extract and separate the 2nd all phase particles out., because adopt the method for under the state that contains indissociable the 2nd phase particle remaining solution being analyzed, if this is worth below 50%, then genuine A value necessarily surpasses 50%, is in the scope of invention of the present invention.As another evaluation method, measure by electric field radioactive Auger electricity optical spectroscopy (FE-AES) and to be present in per unit area and length is whole compositions of the 2nd above phase particle of 0.1 μ m, be 0.1 μ m at area
2In the 2nd above phase particle, be that the number of the particle more than 10 times of the containing ratio of the 3rd groups of elements in the alloy is counted and measured to the containing ratio of the 3rd groups of elements in the 2nd phase particle, try to achieve ratio with respect to all particles number.Make this value be the B value for convenience.And then, ask for the equivalent diameter of the 2nd phase particle,, infer the ratio that the 3rd groups of elements exists as the 2nd phase particle from one by one the particle area and the relation of its composition, if guarantee to measure fully visual field area, confirm that then the material that satisfies the A value roughly satisfies the B value similarly.Here, so-called equivalent diameter is meant the circular diameter that has with by the observed same area of the 2nd particle of section microscope.The A value of each embodiment and each comparative example, the B value, crystal grain diameter (GS), 0.2% yield strength (MPa), the MBR/t value is as shown in table 3 respectively.
Table 3
| ??No. | ??A f(％) | ??E | ????GS(μm) | ????MBR/t | 0.2% yield strength (MPa) | |
| Embodiment | ??1 | ??0.25 | ??0.53 | ????4.3 | ????0.7 | ????851 |
| ??2 | ??0.85 | ??0.43 | ????4.6 | ????0.7 | ????852 | |
| ??3 | ??0.76 | ??0.38 | ????3.7 | ????1.0 | ????881 | |
| ??4 | ??0.53 | ??0.56 | ????2.8 | ????0.7 | ????876 | |
| ??5 | ??0.68 | ??0.61 | ????2.5 | ????1.0 | ????887 | |
| ??6 | ??0.73 | ??0.73 | ????2.6 | ????1.0 | ????886 | |
| ??7 | ??0.46 | ??0.53 | ????3.5 | ????0.7 | ????872 | |
| ??8 | ??0.65 | ??0.58 | ????3.7 | ????0.7 | ????870 | |
| ??9 | ??0.38 | ??0.53 | ????2.8 | ????0.7 | ????887 | |
| ??10 | ??0.55 | ??0.51 | ????2.9 | ????0.7 | ????888 | |
| Comparative example | ??11 | ??0.11 | ??0.45 | ????4.3 | ????0.7 | ????771 |
| ??12 | ??1.25 | ??0.53 | ????4.5 | ????3.5 | ????882 | |
| ??13 | ??0.12 | ??0.88 | ????36 | ????2.1 | ????811 | |
| ??14 | ??1.54 | ??0.68 | ????1.6 | ????1.4 | ????821 | |
| ??15 | ??2.65 | ??0.72 | ????1.4 | ????2.1 | ????822 | |
| ??16 | ??3.76 | ??0.78 | ????1.4 | ????2.8 | ????793 | |
| ??17 | ??4.87 | ??0.82 | ????1.5 | ????3.5 | ????853 | |
| ??18 | ??0.82 | ??0.87 | ????3.3 | ????1?4 | ????836 | |
| ??19 | ??0.78 | ??0.91 | ????2.7 | ????1.4 | ????826 | |
| ??20 | ??0.97 | ??0.93 | ????2.5 | ????2.1 | ????833 |
As shown in table 3, in each embodiment, all be that the MBR/t value is, 0.2% yield strength is more than the 850MPa below 1.0, can realize good bendability and intensity simultaneously.In embodiment the 4th～10, the addition by making Ti significantly improves 0.2% yield strength in particularly preferred scope (2.5～3.5 quality %), and its value becomes more than the 870MPa.By removing Fe, Co adds P to embodiment the 4th～6 outside the Ni respectively in addition; Embodiment the 9th, 10 is respectively by removing V, adds B outside the Zr and makes the further granular of crystal grain, greatly improves 0.2% yield strength, and its value becomes more than the 875MPa.
Then,, go up the W pliability test of carrying out JIS3110 with the bending radius of the long various regulations of 10 wide * 100mm, ask for not producing disruptive minimum bending radius (MBR) in pressure rolling direction and right angle orientation (BadWay) for each embodiment and each comparative example.Bendability is represented by the ratio MBR/t of the relative thickness of slab t of MBR.Intensity is verified the validity of embodiment by measuring 0.2% yield strength.Here, the MBR/t value is more little represents good bendability more.In addition, for the area occupation ratio A of the 2nd phase particle
fWith average mark divergence E, photographed in the surface of each test film and ask for SEM with image processing software, confirm the 2nd phase particle thus.The A of each embodiment and each comparative example
f, E, particle diameter (GS), the MBR/t value, 0.2% yield strength is as shown in table 4 respectively.
Table 4
| ??No. | A value (%) | B value (%) | ??GS(μm) | ????MBR/t | 0.2% yield strength (MPa) | |
| Embodiment | ??1 | ????66 | ????82 | ????4.2 | ????0.7 | ????852 |
| ??2 | ????67 | ????80 | ????4.5 | ????0.7 | ????853 | |
| ??3 | ????70 | ????85 | ????3.6 | ????1.0 | ????880 | |
| ??4 | ????71 | ????84 | ????2.5 | ????0.7 | ????875 | |
| ??5 | ????80 | ????88 | ????2.4 | ????1.0 | ????886 | |
| ??6 | ????81 | ????87 | ????2.3 | ????1.0 | ????888 | |
| ??7 | ????85 | ????90 | ????3.2 | ????0.7 | ????873 | |
| ??8 | ????88 | ????91 | ????3.5 | ????0.7 | ????872 | |
| ??9 | ????90 | ????92 | ????2.7 | ????0.7 | ????886 | |
| ??10 | ????91 | ????93 | ????2.8 | ????0.7 | ????889 | |
| Comparative example | ??11 | ????55 | ????72 | ????4.1 | ????0.7 | ????770 |
| ??12 | ????53 | ????75 | ????4.2 | ????3.5 | ????880 | |
| ??13 | ????- | ????- | ????35 | ????2.1 | ????810 | |
| ??14 | ????70 | ????80 | ????1.5 | ????3.5 | ????822 | |
| ??15 | ????75 | ????81 | ????1.2 | ????3.5 | ????820 | |
| ??16 | ????87 | ????90 | ????1.3 | ????4.3 | ????795 | |
| ??17 | ????90 | ????93 | ????1.2 | ????3.5 | ????854 | |
| ??18 | ????42 | ????61 | ????3.1 | ????2.1 | ????815 | |
| ??19 | ????40 | ????56 | ????2.9 | ????2.1 | ????805 | |
| ??20 | ????35 | ????50 | ????2.7 | ????2.1 | ????812 |
As shown in table 4, in each embodiment, all be that the MBR/t value is, 0.2% yield strength is more than the 850MPa below 1.0, can realize good bendability and intensity simultaneously.Particularly in embodiment the 4th～10, because Ti is in preferred scope (2.5～3.5 quality %), 0.2% yield strength is compared further raising with other embodiment, reaches 870MPa.By removing Fe, Co adds P to embodiment the 4th～6 outside the Ni respectively in addition; Embodiment the 9th, 10 is respectively by removing V, adds B outside the Zr and makes the further granular of crystal grain, and 0.2% yield strength is more than the 880MPa, realizes good intensity.
On the other hand, in each comparative example, the MBR/t value surpasses 1.0 and 0.2% yield strength less than 850MPa, can not realize good bendability and intensity simultaneously.Comparative example the 11st is because the addition of Ti less than 2.0 quality %, can not obtain sufficient 0.2% yield strength.On the contrary, comparative example the 12nd is because the addition of Ti surpasses 4.0 quality %, TiCu
3Thereby separate out bendability is worsened.Comparative example the 13rd is because the 3rd groups of elements of not adding crystal grain granular element, so crystal grain granular not can not obtain sufficient 0.2% yield strength.Comparative example the 13rd is not because form the 2nd phase particle in addition, and thickization of crystal grain can not obtain good bendability.Comparative example the 14th～17 is because the aggregate value of the addition of the 3rd groups of elements surpasses 0.5 quality %, so the 2nd phase particle is exceedingly separated out, bendability worsens.In addition, owing to the Ti that makes in the parent phase that separates out of the 2nd superfluous phase particle loses, the age hardening performance reduces, and can not obtain sufficient 0.2% yield strength.Though the addition of comparative example the 18th～20 the 3rd elements is in suitable scope because the heat-up rate up to the temperature of the complete solid solution of Ti is slower in solution treatment, with the 3rd element be principal constituent the 2nd mutually particle compare TiCu
3It is many that the ratio of separating out separately becomes, its result, and the age hardening performance reduces, and can not obtain sufficient 0.2% yield strength, and bendability is not also in preferred range.
On the other hand, in each comparative example, all be that the MBR/t value surpasses 1.0 and 0.2% yield strength less than 850MPa, can not realize good bendability and intensity simultaneously.Specifically, comparative example the 11st because the amount of Ti less than 2.0 quality %, can not obtain sufficient 0.2% yield strength, be intensity.On the contrary, comparative example the 12nd so the MBR/t value is high, does not obtain good bendability because the amount of Ti surpasses 4.0 quality %.Comparative example the 13rd so the granular of crystal grain is insufficient, does not obtain good intensity because add the element that the 2nd phase particle of the growth that makes inhibition crystal grain is separated out.Comparative example the 13rd is because of thickization of crystal grain, so also do not show good bendability in addition.Comparative example the 14th～17 is being easy to separate out TiCu
3Temperature under carry out (solid solution temperature is 750 ℃ for comparative example the 14th～17, is 800 ℃ for other each embodiment and comparative example).These comparative examples are because the area occupation ratio A of the 2nd phase particle
fSurpass 1.0%, so can not realize good bendability.In addition, owing to the Ti that makes in the parent phase that separates out of the surplus of the 2nd phase particle loses, the age hardening performance reduces, and 0.2% yield strength reduces, and can not realize good intensity.Comparative example the 18th～20th does not carry out sufficient homogenizing annealing and after the hot rolling, air cooling, carries out cold rolling, annealing repeatedly and the material made.Though these comparative example area occupation ratios A
fIn suitable value range, but the unequal distribution of the 2nd phase particle.Therefore, crystal structure becomes mixed grain, can not obtain good bendability and intensity.
As described above described, according to the present invention, by seeking suitableization of Ti amount respectively, suitableization of the amount of the 3rd groups of elements and the 3rd groups of elements be to suitableization of the amount of the 2nd phase particle, and can side by side realize the good bendability and the raising of intensity with high level.The present invention can make the copper alloy that is applicable to connector material etc. thus.
Claims (5)
1. an Albatra metal-, it is the copper base alloy that contains the Ti of 2.0～4.0 quality %, it is characterized in that:, contain the Fe of 0.01～0.5 quality %, Co as the 3rd groups of elements, Ni, Cr, V, Zr, more than one elements among B and the P, the existing as the 2nd phase particle more than 50% of the total amount of the 3rd groups of elements.
2. an Albatra metal-is the copper base alloy that contains the Ti of 2.0～4.0 quality %, it is characterized in that: as the 3rd groups of elements, contain the Fe of 0.01～0.5 quality %, Co, Ni, Cr, V, Zr, more than one elements among B and the P, and then in that observed area is 0.01 μ m by the section microscope
2In the 2nd above phase particle, the containing ratio of the 3rd groups of elements in aforementioned the 2nd phase particle is that the ratio of number of the 2nd phase particle more than 10 times of the containing ratio of the 3rd groups of elements in the alloy is more than 70% of aforementioned the 2nd phase particle integral body.
3. an Albatra metal-is the copper base alloy that contains the Ti of 2.0～4.0 quality %, it is characterized in that: as the 3rd groups of elements, contain the Fe of 0.01～0.5 quality %, Co, Ni, Cr, V, Zr, more than one elements among B and the P, observed area is 0.01 μ m by the section microscope
2The area occupation ratio A of the 2nd above phase particle
fBe below 1.0%.
4. an Albatra metal-is the copper base alloy that contains the Ti of 2.0～4.0 quality %, it is characterized in that: as the 3rd groups of elements, contain the Fe of 0.01～0.5 quality %, Co, Ni, Cr, V, Zr, more than one elements among B and the P are about observed area is 0.01 μ m by the section microscope
2The 2nd above phase particle, defined impartial dispersity E is below 0.8 by following formula.
Di: distance from i the 2nd phase particle to the 2nd nearest phase particle
Ao: measure visual field area
N
A: the number of the 2nd phase particle of in measuring visual field area, being confirmed
5. manufacture method as each described copper alloy of claim 1～4 is characterized in that: have:
At the Fe that in copper, has added 0.01～0.5 quality %, Co, Ni, Cr, V, Zr behind more than one elements among B and the P, adds the Ti of 2.0～4.0 quality %, makes the operation of ingot;
In aforementioned ingot being heated to the solution treatment that arrives temperature T ℃, be heated to the heat-up rate more than 20 ℃/second and surpass 600 ℃ temperature, make it to become the solution treatment operation of supersaturated solid solution afterwards in the temperature province heating of T-100 ℃～T ℃ more than 10 seconds;
Implement cold rolling cold rolling process from the state of aforementioned super saturated solid solution with 5～50% degree of finish;
Aforementioned pressure rolling material is implemented heat treated ageing treatment process down at 350～450 ℃.
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| JP346974/02 | 2002-11-29 | ||
| JP2003018701A JP3748859B2 (en) | 2003-01-28 | 2003-01-28 | High-strength copper alloy with excellent bendability |
| JP18701/03 | 2003-01-28 | ||
| JP18701/2003 | 2003-01-28 |
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| CN102465214A (en) * | 2010-10-29 | 2012-05-23 | Jx日矿日石金属株式会社 | Titan-copper for electric parts |
| CN112210684A (en) * | 2020-10-15 | 2021-01-12 | 台州学院 | Semiconductor target material, equipment of copper-titanium alloy for connector and preparation method |
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|---|---|---|---|---|
| JP4118832B2 (en) * | 2004-04-14 | 2008-07-16 | 三菱伸銅株式会社 | Copper alloy and manufacturing method thereof |
| JP4191159B2 (en) * | 2005-03-14 | 2008-12-03 | 日鉱金属株式会社 | Titanium copper with excellent press workability |
| JP4889801B2 (en) * | 2009-11-25 | 2012-03-07 | Ｊｘ日鉱日石金属株式会社 | Manufacturing method of titanium copper for electronic parts |
| CN102686755A (en) * | 2009-11-25 | 2012-09-19 | Jx日矿日石金属株式会社 | Titanium-copper for electronic component |
| JP5802150B2 (en) * | 2012-02-24 | 2015-10-28 | 株式会社神戸製鋼所 | Copper alloy |
| JP6310131B1 (en) * | 2017-09-22 | 2018-04-11 | Ｊｘ金属株式会社 | Titanium copper for electronic parts |
| CN113005324B (en) * | 2021-02-23 | 2021-12-07 | 江西理工大学 | Copper-titanium alloy and preparation method thereof |
| EP4388142A1 (en) | 2021-08-17 | 2024-06-26 | LN Industries SA | Very high strength copper-titanium alloy with improved formability in the solution annealed temper |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60114542A (en) * | 1983-11-22 | 1985-06-21 | Ngk Insulators Ltd | Age hardenable titanium-copper alloy material |
| JP3763723B2 (en) * | 2000-04-27 | 2006-04-05 | 日鉱金属加工株式会社 | Copper alloy wrought material with excellent bending workability and manufacturing method of copper alloy wrought material |
-
2003
- 2003-11-28 KR KR1020030085596A patent/KR100559814B1/en active IP Right Grant
- 2003-11-28 US US10/722,427 patent/US20040136861A1/en not_active Abandoned
- 2003-12-01 CN CNB2003101195051A patent/CN1297674C/en not_active Expired - Lifetime
-
2008
- 2008-01-29 US US12/022,084 patent/US20080121320A1/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102465214A (en) * | 2010-10-29 | 2012-05-23 | Jx日矿日石金属株式会社 | Titan-copper for electric parts |
| CN112210684A (en) * | 2020-10-15 | 2021-01-12 | 台州学院 | Semiconductor target material, equipment of copper-titanium alloy for connector and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20040048337A (en) | 2004-06-09 |
| US20080121320A1 (en) | 2008-05-29 |
| US20040136861A1 (en) | 2004-07-15 |
| KR100559814B1 (en) | 2006-03-10 |
| CN1297674C (en) | 2007-01-31 |
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