CN1930314A - Copper alloy and process for producing the same - Google Patents
Copper alloy and process for producing the same Download PDFInfo
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- CN1930314A CN1930314A CN 200580007543 CN200580007543A CN1930314A CN 1930314 A CN1930314 A CN 1930314A CN 200580007543 CN200580007543 CN 200580007543 CN 200580007543 A CN200580007543 A CN 200580007543A CN 1930314 A CN1930314 A CN 1930314A
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Abstract
A copper alloy that has a specific chemical composition, the balance being Cu and impurities, in which the relationship between the total number N and the diameter X satisfies the following formula (1). This copper alloy is obtained by cooling a bloom, a slab, a billet or an ingot in at least a temperature range from the temperature of the bloom, the slab, the billet or the ingot just after casting to 450 DEG C, at a cooling rate of 0.5 DEG C/s or more. After the cooling, working in a temperature range of 600 DEG C or lower and further heat treatment of holding for 30 seconds or more in a temperature range of 150 to 750 DEG C are desirably performed. The working and the heat treatment are most desirably performed for a plurality of times. logN 0.4742 + 17.629 exp - 0.1133 X wherein N means the total number of precipitates and inclusions, having a diameter of not smaller than 1 [mu]m which are found in 1 mm 2 of the alloy; and X means the diameter in [mu]m of the precipitates and the inclusions having a diameter of not smaller than 1 [mu]m.
Description
Technical field
The present invention relates to a kind ofly need not solution treatment and can make at an easy rate, and mechanical properties and all excellent copper alloy and the manufacture method thereof of conductivity degree.As the purposes of this copper alloy, can enumerate electric electronic element, security tool etc.
As electric electronic element, for example have following these.In electronic applications, can enumerate: PC junctor, semiconductor block (socket), optical pickup unit (pickup), coaxial connector, IC stop pin (checker pin) etc.Can enumerate in communication field: mobile telephone part (junctor, battery terminal, antenna element), submerged repeater framework, exchange board are with junctor etc.In automotive field, can enumerate: the various electrical element of rly. (relay), various switch (switch), miniature motor (micromotor), dividing plate (diaphragm), various terminal classes etc.In the aerospace field, can enumerate spacecraft take-off and landing device (landing gear) etc.In medical analysis device field, can enumerate: medical connector, industrial junctor etc.In field of household appliances, can enumerate: tame electrical article such as air-conditioning rly., game machine of use optical pickup unit, card connector etc.
As security tool, for example have in ignited in the place of the danger of exploding in existence meetings such as ammunition depot and colliery because of spark, use smash rod and spanner, chain block (chain block), hammer, bottle opener, pliers etc. to pieces.
Background technology
Always, as the copper alloy that is used for described electric electronic element, known have a Cu-Be alloy, and its timeliness with Be is separated out and strengthened, and includes the Be of a great deal of in this alloy.Because the both sides of this strength of alloy and electric conductivity are all excellent, so be widely used with material etc. as spring.Yet, in the manufacturing process of Cu-Be alloy with this alloy is processed in the operation of various parts and can generates the Be oxide compound.
Be is the environmentally harmful material that is only second to Pb, Cd.Particularly, because include the Be of a great deal of in the existing C u-Be alloy, thus in the manufacturing of copper alloy, processing, be necessary to be provided with the treatment process of Be oxide compound, thus manufacturing cost rises, and becomes problem in the recycling process of electric electronic element.So, consider that environmental problem Cu-Be alloy is problematic material.Therefore, environmentally harmful elements such as a kind of Be of making of expectation reduce as far as possible, and all appearance of excellent material of the both sides of tensile strength and electric conductivity.
In patent documentation 1, proposing has a kind of making to be called as the Ni that copper nisiloy (Corson) is
2The copper alloy that Si separates out.This copper nisiloy is an alloy, and tensile strength is 750～820MPa, and electric conductivity is about 40%, and in the alloy that does not contain environmentally harmful elements such as Be, the balance of tensile strength and electric conductivity is fine comparatively speaking.
Yet all there are limitation in this alloy high strengthization and high conductivityization, as follows on the point of model change (variations) residue problem.This alloy is held time hardening, and it comes from Ni
2Si separates out.So, improve electric conductivity if reduce the content of Ni and Si, then tensile strength significantly reduces.On the other hand, in order to increase Ni
2The amount of separating out of Si and make Ni and Si increment goes up on tensile strength and still have limitation, and electric conductivity significantly reduces.Therefore, the copper nisiloy is an alloy, the balance variation of the tensile strength in the zone that zone that its tensile strength is high and electric conductivity are high and electric conductivity, and then model change diminishes.This is based on following reason.
The resistance of alloy (perhaps as its electric conductivity reciprocal) is by electron scattering decision, according to the kind of the element of solid solution in alloy and significantly change.Because the resistance value that makes the Ni of solid solution in alloy rises significantly (electric conductivity is descended significantly), thus be in the alloy at described copper nisiloy, if increment Ni then electric conductivity reduce.On the other hand, the tensile strength of copper alloy obtains by the age hardening effect.The amount of precipitate is many more, and precipitate disperses tricklely more in addition, and tensile strength is just more for improving.The copper nisiloy is that the situation of alloy is because precipitation particles has only Ni
2Si is so aspect the amount of separating out, the aspect of dispersion state, all exist limitation on high strength.
In patent documentation 2, disclose elements such as a kind of Cr of containing, Zr, stipulated the good copper alloy of wire bonding (wire bonding) of surface hardness and surfaceness.Put down in writing as this embodiment, this copper alloy is that prerequisite is made with hot rolling and solution treatment.
But,, need be used to prevent the surface-conditioning of heat cracking and scale removal, thereby productivity reduces in order to carry out hot rolling.In addition, because always in atmosphere, heat, so the easy oxidation of active interpolation element of Si, Mg, Al etc.Therefore, the thick subscale of generation causes a large amount of problems such as deterioration in characteristics of finished product.In addition, in hot rolling and solution treatment, need huge energy.Thus, in the copper alloy of documents 2 records, because with hot-work and solution treatment is prerequisite, so there is problem from the viewpoint of the reduction of manufacturing cost and conserve energy etc., and product performance (except tensile strength and electroconductibility, also having bendability and fatigue characteristic etc.) the such problem of deterioration that causes of the generation etc. that causes thick oxide compound.
On the other hand,, require to have the character of the machinery that is equal to tool steel as described security tool material, for example intensity and wearability, and can not send the spark of the reason that becomes blast, promptly require fire-resistant flower that the property excellence takes place.Therefore, with in the material, adopt the high copper alloy of heat conductivity mostly, particularly separate out and the Cu-Be alloy strengthened with the timeliness of Be at security tool.As previously mentioned, though the Cu-Be alloy is a lot of material of problem on the environment, however, the Cu-Be alloy can a large amount of use of quilt be for following reason with material as security tool.
Fig. 1 is the figure of the relation of expression electric conductivity (IACS (%)) of copper alloy and thermal conduction degree (TC (W/mk)).As shown in Figure 1, both are in 1: 1 relation substantially, improve electric conductivity (IACS (%)) and improve thermal conduction degree (TC (W/mk)), improve fire-resistant flower generation property if in other words then just be.If apply power from the fierceness of hitting etc., then spark takes place when the use of instrument, and this is because allow specific one-tenth divided combustion in the alloy owing to the heat that takes place such as impact.As non-patent literature 1 record, steel is low to moderate below 1/5 of copper because of its thermal conduction degree, rises so the temperature of locality takes place easily.Because steel contains C, so cause "
" reaction and spark is taken place.In fact known, can flashing in the pure iron that does not contain C.Scintillant easily in other the metal, be Ti or Ti alloy.This is because the thermal conductivity of Ti is extremely low, is 1/20 of copper, and cause "
" reaction.Also have, Fig. 1 is the figure that has handled the data shown in the non-patent literature 2.
But, electric conductivity (IACS (%)) and tensile strength (TS (MPa)) are in the relation that is used alternatingly (tradeoff) as described, it is extremely difficult to improve both simultaneously, so all the time, as both having the common high-tensile of tool steel, possess the copper alloy of fully high thermal conduction degree TC again, except described Cu-Be alloy, have no option.
No. 2572042 communique of [patent documentation 1] patent
No. 2714561 communique of [patent documentation 2] patent
[non-patent literature 1] industry heating, vol.36, No.3 (1999), the distribution of (society) Japanese industry stove association, 59 pages
[non-patent literature 2] stretches copper product databook, puts down on August 1st, 9, and the distribution of copper association, 328～355 pages are stretched by Japan
Summary of the invention
First purpose of the present invention is, an Albatra metal-is provided, and its goods change abundant, and ductility and processibility are also excellent, in addition, the security tool desired performance of material, instant heating conductivity, wearability and fire-resistant flower generation property are also excellent.Second purpose of the present invention is, the manufacture method of described copper alloy is provided.
So-called " goods change abundant ", the meaning is by the fine setting addition and/or creates conditions, can be with the balance of electric conductivity and tensile strength, from the Cu-Be alloy with degree or the high level on it, adjust to and existing known copper alloy low-level with degree.
Also have, so-called " balance of electric conductivity and tensile strength and Cu-Be are with degree or the high level on it ", specifically, the meaning is to satisfy the such state of following (a) formula.Below, this state is called as " balance of tensile strength and electric conductivity is good state extremely ".
TS≥648.06+985.48×exp(-0.0513×IACS)…(a)
Wherein, (a) meaning of the TS in the formula is tensile strength (MPa), and the IACS meaning is electric conductivity (%).
About bendability, also preferred and Cu-Be is that the existing alloy of alloy etc. is more than the equal rank.Specifically, test film is implemented 90 ° of pliability tests, measures the radius of curvature R of the minimum that crackle does not take place with various radius-of-curvature, according to the ratio B of itself and thickness of slab t (=R/t) can estimate bendability.The good scope of bendability satisfies B≤2.0 in tensile strength TS is sheet material below the 800MPa, surpass in the sheet material of 800MPa in tensile strength and satisfy following (b) formula.
B≤41.2686-39.4583×exp[-{(TS-615.675)/2358.08}
2]…(b)
In copper alloy, except the characteristic of described such tensile strength TS and electric conductivity IACS, also require wearability as security tool.Therefore, security tool is with under the situation of copper alloy, and it also needs with tool steel equal level is arranged as wearability.Specifically, the hardness under the room temperature is counted more than 250 by Vickers' hardness, has the wearability of this excellence.
The present invention is a main idea with the manufacture method of the copper alloy shown in copper alloy shown in following (A)～(C) and following (D).
(A) Albatra metal-, it is characterized in that, among Zn, Sn, Ag, Mn, Fe, Co, Al, Ni, Si, Mo, V, Nb, Ta, W, Ge, Te and Se, select to add up to more than a kind or 2 kinds 0.1～20 quality %, surplus is made up of copper and impurity, be present in the above particle diameter of the about 1 μ m of particle diameter among precipitate in the alloy and the inclusion, with the total number of precipitate and inclusion, satisfy by the relation shown in following (1) formula.
logN≤0.4742+17.629×exp(-0.1133×X)…(1)
Wherein, the meaning of N is that the total number of the precipitate of per unit area and inclusion is (individual/mm
2), the meaning of X is the particle diameter (μ m) of precipitate and inclusion.
(B) Albatra metal-, it is characterized in that, in quality %, contain from Ti:0.01～5%, any that select among Zr:0.01～5% and Hf:0.01～5%, also contain from Zn, Sn, Ag, Mn, Fe, Co, Al, Ni, Si, Mo, V, Nb, Ta, W, Ge, select to add up to more than a kind or 2 kinds 0.01～20 quality % among Te and the Se, surplus is made up of copper and impurity, be present in the above particle diameter of the about 1 μ m of particle diameter among precipitate in the alloy and the inclusion, with the total number of precipitate and inclusion, satisfy by the relation shown in following (1) formula.
logN≤0.4742+17.629×exp(-0.1133×X)…(1)
Wherein, the meaning of N is that the total number of the precipitate of per unit area and inclusion is (individual/mm
2), the meaning of X is the particle diameter (μ m) of precipitate and inclusion.
(C) Albatra metal-, it is characterized in that, in quality %, contain Cr:0.01～5%, also contain among Zn, Sn, Ag, Mn, Fe, Co, Al, Ni, Si, Mo, V, Nb, Ta, W, Ge, Te and Se and select to add up to more than a kind or 2 kinds 0.01～20 quality %, surplus is made up of copper and impurity, be present in the above particle diameter of the about 1 μ m of particle diameter among precipitate in the alloy and the inclusion, with the total number of precipitate and inclusion, satisfy by the relation shown in following (1) formula.
logN≤0.4742+17.629×exp(-0.1133×X)…(1)
Wherein, the meaning of N is that the total number of the precipitate of per unit area and inclusion is (individual/mm
2), the meaning of X is the particle diameter (μ m) of precipitate and inclusion.
Copper alloy from described (A) to every record of (C), also can contain the part that following unit usually replaces copper again: select among Mg, Li, Ca and the rare earth element add up to 0.001～2 quality % more than a kind or 2 kinds and/or select among P, B, Bi, Tl, Rb, Cs, Sr, Ba, Tc, Re, Os, Rh, In, Pd, Po, Sb, Au, Ga, S, Cd, As and the Pb add up to 0.001～3 quality % more than a kind or 2 kinds.The Be that also can contain 0.1～5 quality % in addition again.These alloys, the maximum value of the average content in the tiny area of its at least a kind of alloying element is preferably more than 1.5 with the ratio of the minimum value of average content.In addition, the crystallization particle diameter of these alloys is preferably 0.01～35 μ m.
(D) manufacture method of an Albatra metal-, this copper alloy is present in the above particle diameter of the about 1 μ m of particle diameter among precipitate in the alloy and the inclusion, satisfies by the relation shown in following (1) formula with the total number of precipitate and inclusion, the manufacture method of this copper alloy is characterised in that, the copper alloy of the chemical constitution of each record melting has from described (A) to (C), the casting sheet that casting is formed, in the temperature province of the casting sheet temperature to 450 after be right after casting at least ℃, with the above speed of cooling cooling of 0.5 ℃/s.
logN≤0.4742+17.629×exp(-0.1133×X)…(1)
Wherein, the meaning of N is that the total number of the precipitate of per unit area and inclusion is (individual/mm
2), the meaning of X is the particle diameter (μ m) of precipitate and inclusion.
Preferably after described cooling,, perhaps implement the thermal treatment of maintenance more than 30 seconds 150 ℃～750 ℃ temperature province again in the processing of the temperature province below 600 ℃.Also can repeatedly implement the processing of the temperature province below 600 ℃ and keep thermal treatment more than 30 seconds, after last thermal treatment, also can carry out the processing of the temperature province below 600 ℃ 150 ℃～750 ℃ temperature province.
So-called in the present invention precipitate is the compound of metal or copper and interpolation element, perhaps adds element compound each other etc., respectively for example: separate out Cu in Ti interpolation material
4Ti, in adding material, Zr separates out Cu
9Zr
2, add precipitating metal Cr in the material at Cr in addition.In addition, so-called inclusion is metal oxide, metallic carbide, metal nitride etc.
Description of drawings
Fig. 1 is the figure of the relation of expression electric conductivity and thermal conduction degree.
Fig. 2 is the figure of the relation of the expression tensile strength of each embodiment and electric conductivity.
Fig. 3 is the mode chart that expression utilizes the castmethod of Du Weili (durville) method.
Among the figure: 1. metal die.
Embodiment
Below, the mode of enforcement of the present invention is described.Also have, in the following description, " % " of each constituent content meaning is " quality % ".
1. copper alloy of the present invention
(a) changing thing forms
Copper alloy of the present invention, have following chemical constitution: contain respectively from Zn, Sn, Ag, Mn, Fe, Co, Al, Ni, Si, Mo, V, Nb, Ta, W, Ge, Te and Se (below, these elements are called " the 1st group element ") among select a kind 0.1～20%, perhaps contain wherein and add up to 0.1～20% more than 2 kinds, surplus is made up of copper and impurity.
These elements all are the balances with the intensity kept and electric conductivity, and make the element of the effect of erosion resistance and thermotolerance raising.This effect adds up at these elements and contains 0.1% and brought into play when above.But when its content was excessive, electric conductivity reduced.Therefore, these elements being contained sometimes, need be 0.1～20% scope at the total content more than a kind or 2 kinds.Particularly because Ag and Sn help high strength by trickle separating out, so preferably utilize energetically.Also have, when containing the 2nd following element, because can guarantee intensity, so the lower value of the 1st element can reduce to 0.01% by the 2nd element.
Alloy of the present invention also can be from the part of following any instead of copper of selection: Ti:0.01～5%, Zr:0.01～5% and Hf:0.01～5%.Also can contain Cr:0.01～5.0%.Below, claim these elements to be " second group element ".
Any that select in Ti:0.01～5%, Zr:0.01～5% and Hf:0.01～5%
Ti, Zr or Hf are because all are elements that tensile strength is improved, so also can make copper alloy of the present invention contain any a kind of these elements.The effect that intensity improves is 0.01% remarkable when above at the content of these elements.But, if its content surpasses 5%, though then intensity rises, the electroconductibility deterioration.In addition, the segregation that the time causes Ti, Zr or Hf in casting is difficult to obtain the casting sheet of homogeneous, in adding thereafter crackle and defective takes place easily man-hour.Therefore, make any a kind of content that contains sometimes of Ti, Zr or Hf all be preferably 0.01～5%.For the balance that obtains tensile strength and electric conductivity good state extremely, these elements are contained more than 0.1%.
Cr：0.01～5％
Cr can not make resistance rise, and is the element that tensile strength is improved.In order to obtain this effect, preferably make it to contain more than 0.01%.Particularly, for obtain with the Cu-Be alloy with the balance of degree or tensile strength more than it and electric conductivity good state very, and preferably make it to contain more than 0.1%.On the other hand, if Cr content surpasses 5%, then Metal Cr is separated out thickly and curved characteristic, fatigue characteristic etc. is brought disadvantageous effect.Therefore, Cr is contained sometimes, preferably its content is 0.01～5%.
Copper alloy of the present invention, purpose for improving hot strength, preferably contain a part that replaces copper as getting off: a kind that selects among Mg, Li, Ca and the rare earth element is respectively 0.001～2%, or adds up to 0.001～2% more than 2 kinds, below, it is called " the 3rd group element ".
Mg, Li, Ca and rare earth element combine with Sauerstoffatom in the copper base material (matrix) and generate trickle oxide compound, are the elements that improves hot strength.This effect is 0.001% remarkable when above at the total content of these elements.But if its content surpasses 2%, then described effect is saturated, and has electric conductivity reduction, the problems such as bendability deterioration of making.Therefore, the total content of selecting among Mg, Li, Ca and the rare earth element to make it to contain more than a kind or 2 kinds sometimes is preferably 0.001～2%.Also have, the rare earth element meaning is Sc, Y and lanthanon, can add the monomer of each element, also can add mishmetal (misch metal) in addition.
Copper alloy of the present invention, the purpose of the liquidus line during for the casting that enlarges alloy and the width (Δ T) of solidus curve, preferably contain a part that replaces copper as getting off: a kind that selects among P, B, Bi, Tl, Rb, Cs, Sr, Ba, Tc, Re, Os, Rh, In, Pd, Po, Sb, Au, Ga, S, Cd, As and the Pb is respectively 0.001～3%, or wherein add up to 0.001～3% more than 2 kinds.Below, be referred to as " four group element ".Also have, Δ T owing to so-called surfusion becomes greatly, still is considered to Δ T under the thermal equilibrium state as benchmark here under the situation of quench solidification.
These elements all have the solidus curve of making to reduce and the effect of expansion Δ T.If this Δ T is big, then can guarantee certain hour to solidifying from the back of casting, therefore casting becomes easily, but if it is expansion that Δ T crosses, then the endurance at low-temperature region reduces, and has latter stage crackle to produce solidifying, and so-called solder embrittlement produces.Therefore, preferred Δ T is 50～200 ℃ a scope.
The element that C, N and O normally contain as impurity.Metallic element in these elements and the alloy forms carbide, nitride and oxide compound.If these precipitates or inclusion are trickle, then with the compound of metal described later or copper and interpolation element, the precipitate that perhaps adds element compound each other etc. is the same, and the reinforcement of alloy is arranged, particularly improve the effect of hot strength, therefore also can add energetically.For example, O forms oxide compound and has the effect that improves hot strength.This effect obtains in containing the alloy of following element easily: Mg, Li, Ca and rare earth element, Al, Si etc. constitute the element of oxide compound easily.But, even this situation also needs the selected residual such condition of solid solution O that do not have.Residual solid solution oxygen becomes H during thermal treatment in nitrogen atmosphere
2O gas and cause and water vapour blast so-called hydrogen disease takes place, bubble (blister) generation of etc.ing and make the quality badness of product, so should be noted that.
If these elements surpass 1% respectively, then become thick precipitate or inclusion, ductility is reduced.Therefore, preferably be limited in below 1% respectively.More preferably below 0.1%.In addition, H is if contain as impurity in alloy, then H
2Gas residue becomes the reason of roll impression etc. in alloy, therefore preferred its content is the least possible
Be can significantly not destroy electric conductivity and the element that helps the precipitation strength of alloy.Preferably make it to contain more than the 0.1 quality % in order to obtain this effect.But if its content surpasses 5%, then not only electric conductivity reduces, and ductility reduces, the processibility deterioration of rolling, bending machining etc.Therefore, Be is contained sometimes, preferably its content is 0.1～5%.
(b) the total number of precipitate and inclusion
In copper alloy of the present invention, be present in particle diameter among precipitate in the alloy and the inclusion be approximately the above particle diameter of 1 μ m, with the total number of precipitate and inclusion, need to satisfy by the relation shown in following (1) formula.
logN≤0.4742+17.629×exp(-0.1133×X)…(1)
Wherein, the meaning of N is that the total number of the precipitate of per unit area and inclusion is (individual/mm
2), the meaning of X is the particle diameter (μ m) of precipitate and inclusion.In (1) formula, the measured value of the particle diameter of precipitate and inclusion more than 1.0 μ m, when being lower than 1.5 μ m, substitution X=1, more than the μ m, when being lower than " α+0.5 " μ m, substitution X=α (α is the integer more than 2) gets final product at " α-0.5 ".
In alloy of the present invention, by making the compound of metal or copper and interpolation element, perhaps add the precipitate of element compound each other etc. and fine separate out, electric conductivity is reduced and intensity is improved.This is to improve intensity by precipitation-hardening.The Cr of solid solution, Ti and Zr reduce owing to separating out, and the electroconductibility of copper base material is near fine copper.
But, if separating out thickly, the particle diameter of the inclusion of these precipitates and metal oxide, metallic carbide, metal nitride etc. reaches more than the 20 μ m, then ductility reduces, and for example has crackle and defective to take place easily when bending machining when being processed into junctor and punching processing.In addition, bring disadvantageous effect can for during use fatigue characteristic and shock-resistant characteristic.Particularly, generate thick Ti-Cr compound during as if the cooling after solidifying, then in manufacturing procedure thereafter, have crackle and defective to produce easily.In addition, because excessively increase,, can not realize the high strength of copper alloy so hinder trickle the separating out of these precipitates etc. by ageing treatment process hardness.Such problem is becoming remarkable under the following situation: among precipitate in being present in alloy and the inclusion particle diameter be approximately particle diameter more than the 1 μ m, with the total number of precipitate and inclusion, when not satisfying concerning shown in described (1) formula.
Therefore in the present invention, be present in particle diameter among precipitate in the alloy and the inclusion and be approximately the above particle diameter of 1 μ m, satisfy by the relation shown in described (1) formula, it is stipulated as necessary important document with the total number of precipitate and inclusion.The total number of preferred precipitate and inclusion has the situation that satisfies the relation shown in following (2) formula, more preferably satisfies the situation of the relation shown in following (3) formula.Also have, the total number of this particle diameter and precipitate and inclusion is tried to achieve according to the method shown in the embodiment.
logN≤0.4742+7.9749×exp(-0.1133×X)…(2)
logN≤0.4742+6.3579×exp(-0.1133×X)…(3)
Wherein, the meaning of N is that the total number of the precipitate of per unit area and inclusion is (individual/mm
2), the meaning of X is the particle diameter (μ m) of precipitate and inclusion.
(c) ratio of the maximum value of the average content in the tiny area of at least a kind of alloying element and the minimum value of content
If the tissue that in copper alloy, has the different zone of concentration of alloying element fine to mix, be that periodic change in concentration produces, then, suppress crystal boundary and move, so there is fine crystalline grain tissue to be easy to obtain such effect because can suppress little diffusion of each element.Consequently, follow the Hall-Petch principle, the intensity ductility of copper alloy improves.So-called tiny area refers to the zone that is made of 0.1～1 μ m diameter, say in fact be X-ray analysis the time the irradiated area The corresponding area.
Also have, the zone that the alloy element concentration among so-called the present invention is different is 2 following kinds.
(1) have the fcc structure identical basically with Cu, but the different state of alloy element concentration.Because the alloy element concentration difference, so, though identical fcc structure is arranged, lattice parameter difference in general, the degree of work hardening is also different certainly.
(2) trickle precipitate dispersive state is arranged in the fcc parent phase.Because it is the alloy element concentration difference, so also different certainly through the dispersion state of the precipitate after the processing thermal treatment.
Average content in the so-called tiny area, the meaning is in X-ray analysis, the value of the analysis area when pooling light beam (beam) footpath below the 1 certain μ m, i.e. mean value in this zone.If X-ray analysis, then preferably has the analytical equipment of field emission type (field emission type) electron beam gun.Analysis means preferably has the analysis gimmick that the concentration cycle is the resolution below 1/5, and more preferably 1/10.Its reason is because if excessive with respect to concentration cycle analysis zone, then integral body averages out, and is difficult to manifest concentration difference.Generally can measure with the x-ray analysis about the 1 μ m of probe (probe) footpath.
The decision material behavior be alloy element concentration and trickle precipitate in the parent phase, the problem among the present invention is to contain the concentration difference of the tiny area of trickle precipitate.Therefore, the signal (signal) from thick precipitate more than the 1 μ m or thick inclusion becomes the interference essential factor.But, from Industrial materials, fully remove thick precipitate or thick inclusion is very difficult, when analyzing, just need to get rid of interference essential factor from described thick precipitate inclusion.Operate as follows for this reason.
That is,, carry out X-ray analysis X, to hold the periodical configuration of concentration with the x-ray analysis equipment about probe diameter 1 μ m at first according to material.Determine analytical procedure as the above-mentioned mode below about 1/5 that makes probe diameter become the concentration cycle.Secondly the decision cycle is the X-ray analysis X length of the above sufficient length that is manifested about 3 times.Carry out the X-ray analysis X of m time (preferred more than 10 times) with this condition, determine the maximum value and the minimum value of concentration according to each X-ray analysis X result.
The number of maximum value and minimum value is m, but the equalization from being worth 2 one-tenth big of cutting-outs respectively.According to more than, can remove the interference essential factor from the signal of above-mentioned thick precipitate inclusion.
According to the ratio of maximum value of having removed described interference essential factor and minimum value, try to achieve concentration ratio.Also have, it tries to achieve concentration ratio and can need not consider the change in concentration of the atom level that the such 10nm degree of spinodal (spinodal) decomposition and trickle precipitate is following according to the alloying element with periodic change in concentration above about 1 μ m.
Thereby the reason that the ductility that fine distributes by alloying element is improved describes in detail a little.If the change in concentration of alloying element takes place, then in the degree of the solution hardening of high density part and lower concentration part material, perhaps as the dispersion state difference of above-mentioned precipitate, so the different in kind of two portions machinery.In such distortion of materials, at first, the lower concentration part that work hardening is soft relatively, next begins the distortion of hard relatively high density part.If in other words,,, show ductility in addition and improve effect so when tensile deformation for example, will demonstrate high stretching then because in material monolithic, cause repeatedly work hardening.So, in the periodic concentration of alloying element changes the alloy that produces, both guaranteed the balance of electric conductivity and tensile strength, again can be when bending machining etc. the favourable high ductibility of performance.
Also have, resistance (inverse of electric conductivity) mainly is corresponding to the at random phenomenon that reduce of electron migration because of solid solution element, because it is to the so almost not influence of micro-defective of crystal grain boundary, so electric conductivity can be owing to described fine grained structure reduces.
The ratio of the maximum value of the average content in the tiny area of at least a kind of alloying element of these effects in parent phase and the minimum value of average content (below, only be called " concentration ratio ".) be 1.5 remarkable when above.Concentration ratio does not have the special stipulation upper limit, still, if concentration ratio is excessive, then probably can't guarantee the fcc structure that the Cu alloy is had, in addition, and the difference of the electrochemical properties possibility that senior general too has the drawback that causes local corrosion etc. easily to occur that becomes.Therefore, concentration ratio is preferably below 20, more preferably below 10.
(d) crystallization particle diameter
If reduce the crystallization particle diameter of copper alloy, then help high strength, and ductility improves also, thus raisings such as bendability.But if the crystallization particle diameter is lower than 0.01 μ m, then hot strength will reduce easily, if surpass then ductility reduction of 35 μ m.Therefore, preferred crystallization particle diameter is 0.01～35 μ m's.Preferred particle diameter is 0.5～30 μ m.0.1～25 μ m most preferably.
2. the manufacture method of copper alloy of the present invention
In copper alloy of the present invention, hinder the compound of metal or copper and interpolation element or add the inclusion of the trickle metal oxide of separating out, metallic carbide, metal nitride etc. of element compound each other etc., be right after the time dot generation of casting sheet after solidifying easily.This inclusion if implement solution treatment after casting, also is difficult to make it solid solution even improve its solid solubility temperature.Solution treatment under the high temperature only can cause aggegation, thickization of inclusion.
Therefore, in the manufacture method of copper alloy of the present invention, melting has the copper alloy of described chemical constitution, at least the temperature province of the casting sheet temperature to 450 ℃ after being right after casting, with the above speed of cooling of 0.5 ℃/s, with the casting sheet cooling of casting gained, make particle diameter among the precipitate that is present in the alloy and the inclusion be approximately particle diameter on the 1 μ m, satisfy by the relation shown in following (1) formula thus with the total number of precipitate and inclusion.
logN≤0.4742+17.629×exp(-0.1133×X)…(1)
Wherein, the meaning of N is that the total number of the precipitate of per unit area and inclusion is (individual/mm
2), the meaning of X is the particle diameter (μ m) of precipitate and inclusion.
After this cooling, preferably implement the processing in the temperature province below 600 ℃, perhaps implement the thermal treatment of maintenance more than 30 seconds 150～750 ℃ temperature province again.Keep thermal treatment more than 30 seconds in the processing of the temperature province below 600 ℃ with 150～750 ℃ temperature province, also can implement repeatedly.In addition, also can after last thermal treatment, be implemented in the processing of the temperature province below 600 ℃.
(a) speed of cooling the temperature province of the casting sheet temperature to 450 ℃ after being right after casting at least: 0.5 ℃/more than the s
The precipitate of the compound of metal or copper and interpolation element or interpolation element compound each other etc. generates in the temperature province more than 280 ℃.Particularly, if the speed of cooling the temperature province of the casting sheet temperature to 450 ℃ after being right after casting is slow, then the inclusion of metal oxide, metallic carbide, metal nitride etc. generates thickly, and its particle diameter even reaches hundreds of μ m more than 20 μ m.In addition, described precipitate also can thickization, reaches more than the 20 μ m.Under the state that has thick like this precipitate and inclusion to generate, not only probably there are man-hour crackle and distortion to take place, and can destroy the precipitation-hardening effect of the described precipitate in the timeliness operation in adding thereafter, can not make alloy high strengthization.Therefore, at least need be in this temperature province with 0.5 ℃/ speed of cooling more than s cooling casting sheet.Speed of cooling is the bigger the better, preferred speed of cooling be 2 ℃/more than the s, more preferably 10 ℃/more than the s.
(b) cooled processing temperature: the temperature province below 600 ℃
According to the manufacture method of copper alloy of the present invention, casting and the casting sheet that obtains, after the defined terms cooling, need not be through the thermal process of hot rolling and solution treatment etc., only making up by processing and aging heat treatment just can become end article.
The processing of rolling, wire drawing etc. is getting final product below 600 ℃.For example, when adopting continuous casting, also can carry out these processing in the process of cooling after solidifying.If process in the temperature province that surpasses 600 ℃, then add man-hour metal or the compound of copper and interpolation element or the precipitate that adds element compound each other etc. separate out thickly, ductility, shock-resistance, the fatigue characteristic of end article are reduced.In addition, if these precipitate is separated out adding man-hour thickly, then just can not fine separate out in ageing treatment, the high strength of copper alloy is with insufficient.
Because processing temperature is low more, the dislocation desity that adds man-hour rises more, so the precipitate that can make the compound of metal or copper and interpolation element or add element compound each other etc. in the ageing treatment of proceeding is more fine separated out.For this reason, can give copper alloy with higher intensity.Therefore, preferred processing temperature is below 450 ℃, more preferably below 250 ℃.Most preferably below 200 ℃.Also can be below 25 ℃.
Also have, the processing of described temperature province, preferably its working modulus (section decrement) is as more than 20% and carry out.More preferably more than 50%.If carry out the processing of such working modulus, because the dislocation of Dao Ruing becomes when ageing treatment and separates out nuclear therefrom, thus the granular of precipitate brought, in addition, make and separate out required time shortening, can realize reduction in early days the deleterious solid solution element of electroconductibility.
(c) ageing treatment condition: keep more than 30 seconds 150～750 ℃ temperature provinces
Ageing treatment is effective aspect following: the precipitate that makes the compound of metal or copper and interpolation element or add element compound each other etc. is separated out and is made the copper alloy high strength, reduces simultaneously to electroconductibility and brings the solid solution element (Cr, Ti etc.) of harm and electric conductivity is improved.But when this treatment temp was lower than 150 ℃, separating out elemental diffusion needed for a long time, and productivity is reduced.Not on the one hand, if treatment temp surpasses 750 ℃, then precipitate becomes too thick, does not only reach the high strength that the precipitation-hardening effect brings, and ductility, shock-resistance and fatigue characteristic reduce.Therefore, preferably carry out ageing treatment 150～750 ℃ temperature province.Preferred aging temperature is 200～700 ℃, more preferably 250～650 ℃.Most preferably 280～550 ℃.
The ageing treatment time is when being lower than 30 seconds, even aging temperature is set highly, can not guarantee the ideal amount of separating out, and then processing costs increases if surpass 72 hours.Therefore, preferably carry out more than 30 seconds 150～750 ℃ temperature province.This treatment time is preferred more than 5 minutes, more preferably more than 10 minutes.Most preferably more than 15 minutes.The upper limit in treatment time does not have special stipulation, but is preferably below 72 hours from the viewpoint of processing costs.Also have, when the timeliness treatment temp is high, can shorten the ageing treatment time.
Also have, the generation of the oxide skin that ageing treatment causes for the oxidation that prevents the surface can be in reducing atmosphere, in the inert gas atmosphere or carry out in the vacuum below the 20Pa.By the processing under atmosphere so, also can guarantee excellent plating.
Described processing and ageing treatment also can be carried out as required repeatedly.If carry out repeatedly, then compared with carrying out handling for 1 time (processing and ageing treatment), can obtain the amount of separating out of wishing in the short period of time, the precipitate that can make the compound of metal or copper and interpolation element or add element compound each other etc. is more fine separated out.At this moment, for example under the situation that 2 times are handled repeatedly,, the 2nd time aging temperature can be reduced (reducing by 20～70 ℃) compared with the 1st time aging temperature.Why carrying out such thermal treatment, is because the 2nd time timeliness thermal treatment temp when high, and the precipitate that generates in the 1st time ageing treatment can thickization.Also with described the same, preferably decrease in the 3rd the later ageing treatment than the aging temperature that carries out before this.In addition, after last thermal treatment, also can be embodied in the processing of the temperature province below 600 ℃.
(d) other
In the manufacture method of copper alloy of the present invention, the condition beyond described the creating conditions, for example the condition to fusion, casting etc. does not limit especially, but, for example gets final product as follows.
Fusion can be to carry out under the atmosphere of non-oxidizable or reductibility.This is because if the solid solution oxygen in the copper water becomes many, then has water vapour to generate in the operation of back and bubbling causes so-called hydrogen disease etc.In addition, if the solid solution element of easy oxidation is arranged, for example the thick oxide compound of Ti, Cr etc. generates, and it is remaining up to finished product, and ductility and fatigue characteristic are reduced significantly.
Obtain casting the method for sheet, based on the viewpoint of productivity and setting rate and preferred continuous casting, still, and if satisfy the method for above-mentioned condition, other method then, for example ingot casting (ingot) method also can.In addition, preferred pouring temperature is more than 1250 ℃.Be more preferably more than 1350 ℃.If this temperature, Cr, Ti and Zr are fully fused, and the precipitate that can not make the compound of inclusion, metal or the copper of metal oxide, metallic carbide, metal nitride etc. and interpolation element in addition or add element compound each other etc. generates.
When obtaining casting sheet,, recommend to adopt the method for the graphite casting mould of carrying out usually in the copper alloy from the viewpoint of oilness by continuous casting.As the casting mold material, main alloying element is the refractory body that is difficult to Ti, Cr or Zr reaction, for example also can use zirconium white (zirconia).
[embodiment 1]
The copper alloy that will have the chemical constitution shown in table 1～3 with the vacuum melting of high-frequency melting stove, is cast in the mold of zirconium white system, obtains the casting sheet of thick 12mm.Rare earth element adds the monomer or the mishmetal of each element.
[table 1]
| Alloy No. | Chemical constitution (quality %, surplus Cu and impurity) | ||||||||||
| First group element | Add up to | Second group element | The 3rd group element | Add up to | The four group element | Add up to | Be | ||||
| Ti | Zr | Hf | Cr | ||||||||
| 1 2 3 4 5 | 15Fe，1.0Si，0.2Sn，1.2Al 10Fe，2.5Ni，1.0Si，0.4Zn 1.01Fe，0.1Zn 0.99Fe，0.5Ag 0.01Sn | 17.4 13.9 1.11 1.49 0.01 | 0.05 0.49 1.02 1.51 1.93 | - - - - - | - - - - - | - - - - - | 0.5Y，0.01Nd，0.02Ca - 0.02Mg - 0.001La | 0.53 - 0.02 - 0.001 | 0.001B - - 0.01P，0.1Bi 0.15Sr，0.5Pd，0.1Os | 0.001 - - 0.11 0.75 | - - - - - |
| 6 * 7 8 9 10 | 5.0Zn，15Fe，5Co，2.0Si 0.2Ta，12Co，1.5Si 2.5Fe，15.5Nb，0.1Ge 0.97Fe，0.5V， 0.3Mo 0.5Fe，0.5Ta | 27.0 * 13.7 18.1 1.77 1.0 | 5.80 * - - - - | - 0.07 0.51 1.02 1.48 | - - - - - | - - - - - | 0.5Nd，0.5Gd，2.0Ca 0.2Sc，0.2Ce - 0.01Mg，0.1Gd 0.01Mg | 3.0 * 0.4 - 0.11 0.01 | 0.5B，0.6Tc 0.1T1，0.5Cs，0.1Po - - 0.011P，1.0Ba，0.1Sb | 1.1 0.7 - - 1.111 | - - - - - |
| 11 12 * 13 14 15 | 1.01Fe，0.1W，0.1Ag 1.5W，0.5Al，0.5Ag 0.4Mo，1.0Co，15Fe，0.4Se 1.0Fe，0.5Si，1.0Nb 0.98Fe，0.2Mo，0.4Zn | 1.21 2.5 16.8 2.5 1.58 | - - - - | 2.01 6.10 *- - - | - - 0.01 0.52 0.99 | - - - - - | - 0.1La，0.01Ca 0.1La，0.01Mg，0.001Li - 0.01Li | - 0.11 0.111 - 0.01 | 0.012B，0.1Re，0.1Tc 0.2Sb 0.1In，0.5Pd，0.1Ga - - | 0.212 0.2 0.7 - - | - - - - - |
| 16 17 18 * 19 20 | 0.99Fe 0.4Si，0.3Sn，1.2V 0.5Fe，1.0Co，0.4Sn 10V， 2.2Co，0.4Ta，0.4Mn，1.0Sn 2.01Fe，0.2Mo，0.5Nb | 0.99 1.9 1.9 14.0 2.71 | - - - - - | - - - - - | 1.48 2.01 6.20 * - - | - - - 0.05 0.50 | 0.01Ca - 0.01Sc，0.1Mg 0.01La - | 0.01 - 0.11 0.01 - | 0.010P，0.02B 0.1Sr，0.2Re 0.9Bi，0.1P 0.1Rh，0.01P - | 0.03 0.3 1.0 0.11 - | - - - - - |
| 21 22 23 24 25 * | 1.0Ni，0.5Si，0.4Sn 0.99Fe 1.0Fe，0.5Sn 12V，15Fe，0.5Mo，1.0Si，1.0Sn 0.99Co，1.02Fe，0.4Sn | 1.9 0.99 1.5 29.5 * 2.41 | - - - - 1.45 | - - - - - | - - - - - | 0.99 1.49 1.99 6.50 * - | 0.02Ca 0.01Li，0.03Ca - 0.1Sc，0.01Mg 0.5Ca，0.8Li，1.5Mg | 0.02 0.04 - 0.11 2.8 * | - 0.011P，1.0Bi 0.01B，0.5Ba，0.5Sb 0.1Au，0.01Po，0.1Cs 0.001B | - 1.011 1.01 0.21 0.001 | - - - - - |
* represent that the present invention stipulates outside the chemical constitution.
[table 2]
| Alloy No. | Chemical constitution (quality %, surplus Cu and impurity) | ||||||||||
| First group element | Add up to | Second group element | The 3rd group element | Add up to | The four group element | Add up to | Be | ||||
| Ti | Zr | Hf | Cr | ||||||||
| 26 27 28 29 30 * | 1.01Nb 0.99Co 0.98Fe 0.5V，0.2Ag 12.5Ni，5.1Si，5.6Nb | 1.01 0.99 0.98 0.7 23.2 * | 1.32 1.22 1.52 1.98 1.55 | - - - - - | - - - - - | - - - - - | - 0.01Mg 0.01Mg - 1.5Mg，1.0La | - 0.01 0.01 - 2.5 * | - - 0.008P，0.01B 0.009Bi 0.5In，1.5Ba，1.0Os | - - 0.018 0.009 3.0 * | - - - - - |
| 31 32 33 34 35 * | 0.95Co 1.00Nb 0.99Fe 0.98Co 1.1V | 0.95 1.00 0.99 0.98 1.1 | - - - - - | 1.11 1.48 1.49 1.52 1.32 | - - - - - | - - - - - | - 0.1La，1.5Ca 0.1Mg，0.5Nd，0.8Li - 0.1La，1.5Rh，2.0Ce | - 1.6 1.4 - 3.6 * | 0.001S - 0.01Cs，0.03Bi 0.01P 1.0Ba，1.3Po，2.0Rh | 0.001 - 0.04 0.01 4.3 * | - - - - - |
| 36 37 38 39 * 40 | 0.99V，0.24Si 1.01Co，2.3Fe，0.4Sn 1.1Nb，0.3Sn，1.2Ni 10.0Co，10.2Fe，0.5Si，4.3W，1.0Mo 0.99Co，0.1Si | 1.23 3.71 2.6 26.0 * 1.01 | - - - - - | - - - - - | 1.52 1.48 1.22 1.38 - | - - - - 1.32 | - - 0.01Li，0.03Gd 0.01Ca，0.1Sc - | - - 0.04 0.11 - | 0.01Bi，0.02Ba，0.001P - - 0.009P - | 0.031 - - 0.009 - | - - - - - |
| 41 * 42 * 43 44 45 | 0.99Nb，0.1Ge 1.01V，0.1Al，0.2Ni 1.00Mo，0.4Zn 1.54Co，0.8Al 0.99Nb，0.4Mn | 1.01 1.31 1.40 2.34 1.39 | - - - - - | - - - - - | - - - - - | 1.42 1.48 1.35 - - | 0.1Ce，0.01Y 0.01Mg - 0.01Nd，0.05Sc - | 0.11 0.01 - 0.06 - | 0.5Sb，1.5Ba，1.0Bi 1.5Rb，1.0Pd 0.012P - 0.01B | 3.0 * 2.5 * 0.012 - 0.01 - | - - - - - - |
| 46 47 48 * 49 50 | 1.52Fe，0.4Te 2.01Fe，0.4Zn 8.0Nb，4.0Si，5.2Ta 14Ni，4Si，1Ag 5.2Mo，3.1V | 1.92 2.41 17.2 19 8.3 | - - - - - | - - - - - | - - - - - | - - - - - | 0.01Mg，005Y，0.001Li - 0.7La，0.5Ca，1.2Sc 0.01Nd，0.05Y - | 0.061 - 2.4 * 0.06 - | 0.011Pd，0.1Re - - - 0.01P，0.1Ba | 0.11 - - - 0.11 | - - - - - |
* represent that the present invention stipulates outside the chemical constitution.
[table 3]
| Alloy No. | Chemical constitution (quality %, surplus Cu and impurity) | ||||||||||
| First group element | Add up to | Second group element | The 3rd group element | Add up to | The four group element | Add up to | Be | ||||
| Ti | Zr | Hf | Cr | ||||||||
| 51 52 53 54 55 * | 10.1W，4.2Ge 2.5Co 1.54Fe 1.24V 10.2Fe，7.8Co，3.4Zn，3.2Al，3.8W | 14.3 2.5 1.54 1.24 28.4 * | - - - - - | - - - - - | - - - - - | - - - - - | 0.1Ce，0.01La 0.01Mg - 0.001Li - | 0.11 0.01 - 0.001 - | 0.1Sr，0.1Os - 0.001B 0.01Bi - | 0.2 - 0.001 0.01 - | - - - - - |
| 56 57 58 59 60 | 0.5Fe，0.5Co，0.5Ag 0.4Sn，1.0Fe 0.25Ta，0.3Nb 0.5Mo，0.1Fe 0.5Fe，0.1Si，0.2Sn | 1.5 1.4 0.55 0.6 0.8 | 3.00 4.00 - - 1.50 | - - 2.50 4.00 - | - - - - - | - - - - - | - 0.1Sc，0.1Ca 0.01Nd，0.1La - 0.2Ca | - 0.2 0.11 - 0.2 | 0.1Ba，0.01Os - 0.1Pd，0.05Bi 0.01P，0.1Re 0.01P，0.1S | 0.11 - 0.15 0.11 0.11 | - - - - - |
| 61 62 63 64 65 | 0.6Ag，4.0Co 1.0Zn，1.0Ag，3.0Nb 2.0Fe，0.5Ta 0.4Ag 1.0Sn，2.5Fe，3.0Se | 4.6 5.0 2.5 0.4 6.5 | - - - - - | - - - - - | - - - - - | - - - 2.50 - | - 0.5Mg，0.1Gd - - 0.01Nd | - 0.6 - - 0.01 | - - 0.1P，0.01B - 0.25B，0.001Tl | - - 0.11 - 0.251 | 0.4 2.1 0.5 2.1 0.6 |
| 66 67 68 69 70 | 2.0Sn，0.1Al，0.1Si 0.2Sn，0.4Te 0.1Ag，0.3Fe，0.5Mo，0.2Se 0.5Sn，0.1Ag 0.5Ta | 2.2 0.6 1.1 0.6 0.5 | - 0.50 0.20 1.00 - | 0.01 - 0.20 2.00 0.30 | - - - - - | 2.50 - - - - | 0.1Y，0.5Sc 0.1Ca - - 0.1Gd | 0.6 0.1 - - 0.1 | 0.5Sb 0.01P，0.1B，0.001Ga - 0.3B，0.1Re，0.2Rh - | 0.5 0.111 - 0.6 - | 2.3 2.8 0.6 2.8 2.6 |
* represent that the present invention stipulates outside the chemical constitution.
With the casting sheet that obtains, from 950 ℃ to 450 ℃ temperature province, by the speed of cooling cooling of spray cooling with regulation as the temperature after being right after casting (temperature after mold takes out just).The temperature variation in the place of the thermocouple needle flow measurement regulation by embedding mold is deviate from surface temperature behind the mold with contact temperature counting point measuration casting sheet.According to the also usefulness of these results and the parsing of conducting heat, calculate the average cooling rate on the casting sheet surface that reaches 450 ℃.Solidify starting point and be the molten metal 0.2g for preparing each composition, by trying to achieve with the heat analysis in the continuous cooling of the speed of regulation.
Be made into the rolling blank of thick 10mm * wide 80mm * long 150mm by cut-out and cutting from the casting sheet that obtains.To the rolling blank of a part, carry out solution heat treatment in order to compare with 950 ℃.To rolling (the 1st time is rolling) that these rolling blanks are at room temperature implemented draft 80%, become the sheet material of thick 2mm, implement ageing treatment (the 1st timeliness) and be made into to supply the examination material with defined terms.For the confession examination material of a part, rolling (the 2nd time rolling) that at room temperature carry out draft 95% again becomes thick 0.1mm, carries out ageing treatment (the 2nd timeliness) with defined terms.These create conditions table 4～7 demonstrations.
That so makes according to following method, tries to achieve the particle diameter of precipitate and inclusion and total number, tensile strength, electric conductivity and the bendability of per unit area for trying in the material.With these as a result merge record in table 4～7.
The total number of＜precipitate and inclusion 〉
Mirror ultrafinish directly with this state, or after carrying out etch by ammonia soln, is observed the visual field of 1mm * 1mm perpendicular to each rolling surface and section parallel with rolling direction for the examination material with 100 times multiplying power by opticmicroscope.Thereafter, measure precipitate and inclusion major diameter (on the way not with condition that crystal boundary contact under in intragranular the longest approaching collinear length) and the value defined that obtains is a particle diameter.In (1) formula, when the measured value of the particle diameter of precipitate and inclusion more than 1.0 μ m, when being lower than 1.5 μ m, substitution X=1, more than the μ m, when being lower than " α+0.5 " μ m, substitution X=α (α is the integer more than 2) gets final product at " α-0.5 ".In addition,, be in 1 of conduct in the closed line, calculate the total number n with report to the leadship after accomplishing a task 1/2 of the conduct of closed line in 1mm * 1mm visual field of each particle diameter
1, number the N (=n in optional 10 visuals field
1+ n
2+ ... + n
10) mean value (N/10), be defined as this test portion each the precipitate of particle diameter and the total number of inclusion.
＜concentration ratio 〉
Grind the section of alloy, with the beam diameter of 0.5 μ m, 2000 times the visual field is to carrying out X-ray analysis X by X-ray analysis at random 10 times to 50 μ m length, tries to achieve the maximum value and the minimum value of the content of each alloying element in each the X-ray analysis X.Big 2 of the value of removing in maximum value and minimum value respectively try to achieve the mean value of maximum value and minimum value in remaining 8 times, with its ratio as concentration ratio and calculate.
＜tensile strength 〉
For the examination material,,, try to achieve the tensile strength (TS (MPa)) under the room temperature (25 ℃) from described according to the method for JIS Z 2241 regulations so that the draw direction mode parallel with rolling direction extracted the 13B test film that is defined as JIS Z 2201.
＜electric conductivity 〉
For the examination material, so that the length direction mode parallel with rolling direction taked the test film of wide 10mm * long 60mm, at the length direction circulating current of test film, the potential difference at the two ends of determination test sheet is tried to achieve resistance according to 4 terminal methods from described.Then, calculate the resistance (resistivity) of per unit volume, according to trying to achieve electric conductivity (IACS (%)) with the ratio of the resistivity 1.72 μ Ω cm of the standard test portion of many crystallizations of annealing fine copper according to volume by the test film of micrometer (micrometer) metering.
＜bendability 〉
For the examination material,, change the radius-of-curvature (internal diameter) of bend from described, implement 90 ° of pliability tests so that the length direction mode parallel with rolling direction taked the test film of a plurality of wide 10mm * long 60mm.Use opticmicroscope, the bend of the test film after the outside diameter viewing test.Then, the radius-of-curvature that will not have the minimum that crackle takes place is as R, try to achieve its with the ratio B of the thickness t of test film (=R/t).
[table 4]
| Distinguish | Alloy No. | Create conditions | ① | ② | Crystallization particle diameter (μ m) | Characteristic | ||||||||||||
| Speed of cooling (℃/s) | For the first time rolling | Thermal treatment for the first time | Second this is rolling | Second this thermal treatment | Tensile strength (MPa) | Electric conductivity (%) | Bendability | |||||||||||
| Temperature (℃) | Thickness (mm) | Temperature (℃) | Time | Temperature (℃) | Thickness (mm) | Temperature (℃) | Time | B (R/t ) | Estimate | |||||||||
| Example of the present invention | 1 2 3 4 5 | 1 2 3 4 5 | 9 10 10 11 11 | 25 25 25 25 25 | 2.0 2.0 2.0 2.0 2.0 | 400 400 400 400 400 | 2h 2h 2h 2h 3h | 25 25 25 25 25 | 0.1 0.1 0.1 0.1 0.1 | 350 350 350 350 350 | 10h 10h 10h 10h 10h | △ ◎ ◎ ◎ ○ | 10.5(Fe) 10(Fe)，1.5(Si) 3.2(Ti) 2.5(Ti) 3.1(Ti) | 30 14 10 8 0.1 | 905 1020 1169 1301 1409 | 23 26 17 10 6 | 2 2 2 3 5 | ○ ○ ○ ○ ○ |
| 6 7 8 9 10 | 7 8 9 10 11 | 10 10 11 10 10 | 25 25 25 25 25 | 2.1 1.9 2.0 2.0 2.0 | 400 400 400 400 400 | 2h 2h 2h 2h 3h | 25 25 25 25 25 | 0.1 0.1 0.1 0.1 0.1 | 350 350 350 350 350 | 10h 10h 10h 10h 10h | △ ◎ ◎ ◎ ○ | 2.4(Si) 12(Nb)，2.5(Fe) 1.8(Zr) 2.5(Zr) 5.6(Zr) | 20 25 15 8 1 | 910 1019 1173 1295 1439 | 21 26 16 10 4 | 2 2 3 5 5 | ○ ○ ○ ○ ○ | |
| 11 12 13 14 15 | 13 14 15 16 17 | 10 10 11 9 9 | 25 25 25 25 25 | 2.0 1.9 2.0 1.9 1.9 | 400 400 400 400 400 | 2h 2h 2h 2h 3h | 25 25 25 25 25 | 0.1 0.1 0.1 0.1 0.1 | 350 350 350 350 350 | 10h 10h 10h 10h 10h | △ ◎ ◎ ◎ ○ | 5.2(Fe) 1.5(Nb)，1.2(Fe) 1.8(Fe)，1.5(Zn) 1.8(Hf) 2.8(Hf) | 30 16 12 5 0.2 | 890 1050 1172 1293 1439 | 25 25 17 11 5 | 2 2 3 5 5 | ○ ○ ○ ○ ○ | |
| 16 17 18 19 20 | 19 20 21 22 23 | 11 11 10 10 10 | 25 25 25 25 25 | 2.0 2.0 2.0 2.0 2.0 | 400 400 400 400 400 | 2h 2h 2h 2h 2h | 25 25 25 25 25 | 0.1 0.1 0.1 0.1 0.1 | 350 350 350 350 350 | 10h 10h 10h 10h 10h | △ ◎ ◎ ◎ ◎ | 12.5(V) 3.9(Ti) 2.3(Ni)，1.5(Si) 1.8(Fe) 1.9(Fe) | 16 33 35 28 19 | 900 782 780 865 954 | 25 54 55 40 30 | 1 1 1 2 2 | ○ ○ ○ ○ ○ | |
| 21 22 23 24 25 | 24 26 27 28 29 | 10 10 10 9 11 | 25 25 25 25 25 | 2.0 2.0 2.0 2.0 2.0 | 400 400 400 400 400 | 2h 2h 2h 2h 2h | 25 25 25 25 25 | 0.1 0.1 0.1 0.1 0.1 | 350 350 350 350 350 | 10h 10h 10h 10h 10h | ◎ ◎ ◎ ◎ ○ | 11.9(V) 5.9(Ti) 3.5(Ti)，1.5(Co) 3.8(Ti)，1.6(Fe) 5.2(Ti)，1.5(Ag) | 12 10 9 10 0.5 | 1000 1230 1209 1290 1405 | 22 15 18 10 6 | 2 2 3 3 5 | ○ ○ ○ ○ ○ | |
" h " the expression time (hours) of " time ".
1. " △ ", " zero " and " ◎ " represent to satisfy (1) formula, (2) formula and (3) formula respectively.
2. expression " microsegregation (minimum value of the maximum value/content of content) ".It in the bracket object elements.
The relation of (b) formula regulation is satisfied in " zero " expression of the evaluation of " bendability ".
[table 5]
| Distinguish | Alloy No. | Create conditions | ① | ② | Crystallization particle diameter (μ m) | Characteristic | ||||||||||||
| Speed of cooling (℃/s) | For the first time rolling | Thermal treatment for the first time | Second this is rolling | Thermal treatment for the second time | Tensile strength (MPa) | Electric conductivity (%) | Bendability | |||||||||||
| Temperature (℃) | Thickness (mm) | Temperature (℃) | Time | Temperature (℃) | Thickness (mm) | Temperature (℃) | Time | B (R/t) | Estimate | |||||||||
| Example of the present invention | 26 27 28 29 30 | 31 32 33 34 36 | 9 10 10 10 11 | 25 25 25 25 25 | 2.0 1.9 2.0 2.0 2.0 | 400 400 400 400 400 | 2h 2h 2h 2h 2h | 25 25 25 25 25 | 0.1 0.1 0.1 0.1 0.1 | 350 350 350 350 350 | 10h 10h 10h 10h 10h | ◎ ◎ ◎ ◎ ◎ | 1.7(Zr) 2.1(Zr) 2.2(Zr) 2.5(Zr) 2.0(Zr) | 10 2 4 2 2 | 1240 1302 1298 1300 1290 | 15 10 11 10 10 | 2 3 2 3 3 | ○ ○ ○ ○ ○ |
| 31 32 33 34 35 | 37 38 40 43 44 | 10 9 10 9 10 | 25 25 25 25 25 | 2.0 1.9 2.0 2.0 2.0 | 400 400 400 400 400 | 2h 2h 2h 2h 2h | 25 25 25 25 25 | 0.1 0.1 0.1 0.1 0.1 | 350 350 350 350 350 | 10h 10h 10h 10h 10h | ◎ ◎ ◎ △ ◎ | 13.0(Hf) 2.9(Hf) 2.5(Hf) 3.5(Cr) 5.2(Co)，1.5(Al) | 5 12 28 27 15 | 1230 1190 800 815 1005 | 15 15 60 30 35 | 3 2 1 1 1 | ○ ○ ○ ○ ○ | |
| 36 37 38 39 40 | 45 46 47 49 50 | 10 9 10 10 9 | 25 25 25 25 25 | 2.0 2.0 2.0 2.0 2.0 | 400 400 400 400 400 | 2h 2h 2h 2h 2h | 25 25 25 25 25 | 0.1 0.1 0.1 0.1 0.1 | 350 350 350 350 350 | 10h 10h 10h 10h 10h | △ △ ◎ △ ◎ | 1.5(Nb) 12.6(Fe) 3.2(Fe) 5.2(Ni)，2.4(Si) 15.2(Mo)，7.8(V) | 25 24 12 8 12 | 836 928 1014 1220 1198 | 26 18 21 10 26 | 1 1 2 3 2 | ○ ○ ○ ○ ○ | |
| 41 42 43 44 45 | 51 52 53 54 56 | 9 10 11 11 9 | 25 25 25 25 25 | 2.0 2.0 2.0 2.0 2.0 | 400 400 400 400 400 | 2h 2h 2h 2h 2h | 25 25 25 25 25 | 0.1 0.1 0.1 0.1 0.1 | 350 350 350 350 350 | 10h 10h 10h 10h 10h | △ ◎ ◎ ◎ ◎ | 21(W)，1.8(Ge) 5.8(Co) 2.8(Fe) 5.2(Co)，2.5(Al) 5.2(Ti) | 2 10 20 21 1 | 1320 1030 862 810 1310 | 5 29 40 49 12 | 4 3 1 1 4 | ○ ○ ○ ○ ○ | |
| 46 47 48 49 50 | 57 58 59 60 61 | 10 9 9 10 9 | 25 25 25 25 25 | 2.0 2.0 2.0 2.0 2.0 | 400 400 400 400 400 | 2h 2h 2h 2h 2h | 25 25 25 25 25 | 0.1 0.1 0.1 0.1 0.1 | 350 350 350 350 350 | 10h 10h 10h 10h 8h | ○ ○ ○ ○ ◎ | 10.2(Ti) 5.2(Zr) 8.2(Zr) 3.0(Ti) 3.2(Co) | 0.5 0.1 0.3 5 20 | 1456 1325 1485 1100 820 | 8 15 6 23 40 | 5 4 5 2 1 | ○ ○ ○ ○ ○ | |
" h " the expression time (hours) of " time ".
1. " △ ", " zero " and " ◎ " represent to satisfy (1) formula, (2) formula and (3) formula respectively.
2. expression " microsegregation (minimum value of the maximum value/content of content) ".It in the bracket object elements.
The relation of (b) formula regulation is satisfied in " zero " expression of the evaluation of " bendability ".
[table 6]
| Distinguish | Alloy No. | The part of creating conditions | ① | ② | Crystallization particle diameter (μ m) | Characteristic | |||||||||||||||
| Speed of cooling (℃/s) | For the first time rolling | Thermal treatment for the first time | For the second time rolling | Thermal treatment for the second time | Rolling for the third time | Thermal treatment for the third time | Tensile strength (MPa) | Electric conductivity (%) | Crooked | ||||||||||||
| Temperature (℃) | Thickness (mm) | Temperature (℃) | Time | Temperature (℃) | Thickness (mm) | Temperature (℃) | Time | Temperature (℃) | Thickness (mm) | Temperature (℃) | Time | B (R/t) | |||||||||
| Example of the present invention | 51 52 53 54 55 | 62 63 64 65 66 | 10 10 10 10 10 | 25 25 25 25 25 | 2.0 2.0 2.0 2.0 2.0 | 400 400 400 400 400 | 2h 2h 2h 2h 2h | 25 25 25 25 25 | 0.1 0.1 0.1 0.1 0.1 | 350 350 350 350 350 | 8h 8h 8h 8h 8h | - - - - - | - - - - - | - - - - - | - - - - - | ◎ ◎ ◎ ◎ ◎ | 10.2(Nb)，1.5(Zn) 2.5(Fe) 5.9(Cr) 4.8(Fe) 1.5(Sn) | 15 25 12 22 3 | 1160 840 1156 870 1200 | 17 40 17 38 16 | 2 1 3 1 2 |
| 56 57 58 59 60 | 67 68 69 70 3 | 10 10 10 10 10 | 25 25 25 25 580 | 2.0 2.0 2.0 2.0 3.0 | 400 400 400 400 - | 2h 2h 2h 2h - | 25 25 25 25 25 | 0.1 0.1 0.1 0.1 1.0 | 350 350 350 350 450 | 8h 8h 8h 8h 1.5h | - - - - 25 | - - - - 0.1 | - - - - 350 | - - - - 5h | ◎ ◎ ○ ○ ◎ | 1.5(Be) 1.5(Be)，1.5(Fe) 1.8(Zr) 5.4(Be) 2.5(Ti) | 0.5 14 0.01 0.05 15 | 1350 1000 1530 1500 1040 | 14 29 12 12 20 | 4 1 5 5 1 | |
| 61 62 63 64 65 | 3 3 3 4 4 | 10 10 10 10 10 | 250 580 250 500 200 | 3.0 3.0 3.0 3.0 3.0 | 700 600 - - 700 | 0.5h 1h - - 0.5h | 25 25 25 25 25 | 1.0 1.0 1.0 1.0 1.0 | 450 450 450 450 450 | 1.5h 1.5h 1.5h 1.5h 1.5h | 25 25 25 25 25 | 0.1 0.1 0.1 0.1 0.1 | 350 350 350 350 350 | 5h 5h 5h 5h 5h | ◎ ◎ ◎ ◎ ◎ | 2.3(Ti) 2.5(Ti) 3.0(Ti) 2.7(Ti) 2.5(Ti) | 7 6 13 12 6 | 1050 1060 1100 1090 1110 | 21 22 18 12 13 | 1 1 1 1 1 | |
| 66 67 | 4 4 | 10 10 | 500 250 | 3.0 3.0 | 600 - | 1h - | 25 25 | 1.0 1.0 | 450 450 | 1.5h 1.5h | 25 25 | 0.1 0.1 | 350 350 | 5h 5h | ◎ ◎ | 2.8(Ti) 3.2(Ti) | 5 12 | 1100 1150 | 11 14 | 1 1 | |
" h " the expression time (hours) of " time ".
1. " zero " and " ◎ " represent to satisfy (2) formula and (3) formula respectively.
2. expression " microsegregation (minimum value of the maximum value/content of content) ".It in the bracket object elements.
The relation of (b) formula regulation is satisfied in " zero " expression of the evaluation of " bendability ".
[table 7]
| Distinguish | Alloy No. | Create conditions | ① | ② | Crystallization particle diameter (μ m) | Characteristic | Solution treatment | ||||||||||||
| Speed of cooling (℃/s) | For the first time rolling | Thermal treatment for the first time | For the second time rolling | Thermal treatment for the second time | Tensile strength (MPa) | Electric conductivity (%) | Bendability | ||||||||||||
| Temperature (℃) | Thickness (mm) | Temperature (℃) | Time | Temperature (℃) | Thickness (mm) | Temperature (℃) | Time | B (R/t) | Estimate | ||||||||||
| Comparative example | 1 2 3 4 5 | 6 * 12 * 18 * 25 * 26 | 11 10 10 10 10 | 25 25 25 25 25 | 2.0 2.0 1.9 1.9 2.0 | - - - 400 400 | - - - 2h 2h | - - - 25 25 | - - - 0.1 0.1 | - - - 350 350 | - - - 10h 10h | - - - × × | - - - - 0.1(Ti) | - - - 9 25 | - - - 1250 750 | - - - 5 25 | - - - 6 6 | - - - × × | ----have |
| 6 7 8 9 10 | 30 * 33 33 34 35 * | 10 0.3 * 10 10 10 | 25 25 800 * 25 25 | 2.0 2.0 2.0 2.0 2.0 | 400 400 400 400 400 | 2h 2h 2h 2h 2h | 25 25 25 25 25 | 0.1 0.1 0.1 0.1 0.1 | 350 350 - 350 350 | 10h 10h - 10h 10h | × × - × × | - - - 0.05(Zr) - | 3 4 - 32 8 | 1310 720 - 720 1110 | 2 20 - 34 8 | 7 5 - 5 5 | × × - × × | ---have- | |
| 11 12 13 14 15 | 37 39 * 41 * 42 * 43 | 10 10 9 9 9 | 25 25 25 25 25 | 2.0 2.0 1.9 2.0 2.0 | 400 400 400 400 400 | 2h 2h 2h 2h 2h | 25 25 25 25 25 | 0.1 0.1 0.1 0.1 0.1 | 350 350 350 350 350 | 10h 10h 10h 10h 10h | × × × × × | 0.11(Hf) - - - 0.9(Mo) | 28 10 26 26 35 | 690 1210 820 873 692 | 38 5 22 20 46 | 4 6 4 4 5 | × × × × × | Have---have | |
| 16 17 | 48 * 55 * | 10 10 | 25 25 | 2.0 2.0 | 400 - | 2h - | 25 - | 0.1 - | 350 - | 10h - | × - | - - | 10 - | 1200 - | 2 - | 6 - | × - | - - | |
" h " the expression time (hours) of " time ".
The relation of the foot with thumb down of " * " 1. (1)～(3) formula regulation.
2. expression " microsegregation (minimum value of the maximum value/content of content) ".It in the bracket object elements.
The relation of (b) formula regulation is satisfied in " zero " expression of the evaluation of " bendability ".
" evaluation " on bendability one hurdle, in tensile strength TS is sheet material below the 800MPa, satisfy B≤2.0, surpass in tensile strength and to be " zero " when satisfying following (b) formula in the sheet material of 800MPa, be when not satisfying " * ".
B≤41.2686-39.4583×exp[-{(TS-615.675)/2358.08}
2]…(b)
Fig. 2 is the figure of the relation of the expression tensile strength of each embodiment and electric conductivity.As table 4～7 and shown in Figure 2, in example 1～76 of the present invention, because chemical constitution, concentration ratio also have the total number of precipitate inclusion to be in the scope of the present invention's regulation, so tensile strength and electric conductivity satisfy described (a) formula.Therefore, these alloys, the balance of its electric conductivity and tensile strength considered to be in Be adds copper alloy equal extent or the high level on it.So as can be known, copper alloy of the present invention, the variation of its tensile strength and electric conductivity (variations) is abundant.In addition, example 1,6,11,16,34,36,37,39,41,64,65 and 66 of the present invention is with addition and/or create conditions and carried out the example of inching in same constituent class.About these alloys, have the tensile strength shown in " △ " among Fig. 2 and the relation of electric conductivity, be considered to have the copper alloy of the characteristic of known copper alloy always.Curved characteristic is also good.
On the other hand, comparative example 1～4,6,10,12～14,16 and 17, the content of any one has all broken away from the scope of the present invention's regulation, the comparative example 1～3 and 17 that bendability is poor, electric conductivity is low, because the 2nd time rolling in raw edges serious and can't carry out test portion and take, so do not arrive evaluating characteristics.In addition, implemented the comparative example 5,9,11 and 15 of 950 ℃ solution treatment, its tensile strength is poor, and bendability is also bad.
[embodiment 2]
In order to estimate the application on security tool, make test portion by the following method, estimate abradability (Vickers' hardness) and fire-resistant flower generation property.
The alloy that will have the chemical ingredients shown in the table 8 fuses with high frequency furnace in atmosphere, carries out the metal die casting according to Du Weilifa.Promptly; under the state shown in Fig. 3 (a), keep metal die 1, with wooden carbon dust guarantee reducing atmosphere on one side, on one side with behind about 1300 ℃ molten metal injection metal die 1; it with the appearance shown in Fig. 3 (b) upset, is made it to solidify and make the casting sheet with the state shown in Fig. 3 (c).Metal die 1 is the cast iron of thick 50mm, and its inside offers cooling and uses the hole, can be with air cooled mode pipe arrangement.The casting sheet is a wedge shape so that cast easily, and following section is 30 * 300, and last section is 50 * 400mm, and height is 700mm.
Take from the lower end of the casting sheet that obtains after the surface grinding, to implement cold rolling ((375 ℃ * 16h), obtain the plate of thick 10mm of 30 → 10mm) → thermal treatments to the part of 300mm.Use these plates, according to total number, tensile strength, electric conductivity and the bendability of described method investigation precipitate and inclusion, in addition, according to following method investigation wearability, thermal conduction degree and fire-resistant flower generation property.Table 8 shows these results.
＜wearability 〉
From taking the test film of wide 10mm * long 10mm respectively for the examination material, mirror ultrafinish is perpendicular to rolling surface and the section parallel with rolling direction, according to the method that JIS Z 2244 stipulates, measures Vickers' hardness under 25 ℃, load 9.8N.
＜thermal conduction degree 〉
Thermal conduction degree (TC (W/mK)) is to try to achieve described electric conductivity (IACS (%)) according to the formula of putting down in writing among Fig. 1 " TC=14.804+3.8172 * IACS ".
＜fire-resistant flower generation property 〉
Use the bench grinding machine (bench grinder) of rotating speed, carry out spark test, have sparkless to take place by Visual Confirmation according to the method for JIS G 0566 regulation as 12000rpm.
Also have, thermopair is inserted the position thermometric of 5mm under the mold inner-wall surface of 100mm position from section down, the average cooling rate to 450 ℃ of trying to achieve based on the liquidus line that is obtained by Calculation of Heat Transfer is 10 ℃/s.
[table 8]
| Distinguish | Chemical constitution (quality %, surplus: Cu and impurity) | ① | Crystallization particle diameter (μ m) | Tensile strength (MPa) | Electric conductivity (%) | Bendability | Wearability (Hv) | Thermal conduction degree (W/mK) | There is sparkless to take place | |||||||
| Hf | Ti | Zr | Sn | Mg | P | B (R/t) | Estimate | |||||||||
| Example of the present invention | 68 69 70 | - - 2.0 | - 1.5 - | 1.0 - - | 0.5 0.4 1.2 | 0.01 - 0.1 | 0.01 0.05 - | ◎ ◎ ◎ | 25 12 20 | 1110 1058 998 | 32 29 35 | 2 2 2 | ○ ○ ○ | 342 327 310 | 137 126 148 | Do not have |
| Comparative example | 18 19 | - - | 5.4 * - | - 6.0 * | - 1.5 | 0.001 0.1 | 0.1 - | × × | 2 1 | 1402 1395 | 1 1 | 6 6 | × × | 426 424 | 19 19 | Have |
1. (3) formula is satisfied in " ◎ " expression, the relation of " * " foot with thumb down (1)～(3) formula regulation.
" relation of satisfied (b) formula regulation of " zero " expression that " bendability " estimated, " * " foot with thumb down.
As shown in table 8, in example 68～70 of the present invention, excelling in abrasion resistance, thermal conductivity is also big, does not observe spark.On the other hand, comparative example 18 and 19 is because the relation of the chemical constitution of all discontented unabridged version invention regulation and (1) formula regulation so thermal conductivity is little, can be observed spark.
[industrial utilize possibility]
According to the present invention, one Albatra metal-and manufacture method thereof can be provided, and it makes the variation of goods abundant, and elevated temperature strength and processability are also excellent in addition, security tool is with material desired performance in addition, and namely that property occurs is also excellent for pyroconductivity, mar proof and fire-resistant flower.
Claims (13)
1. an Albatra metal-, it is characterized in that, contain select among Zn, Sn, Ag, Mn, Fe, Co, Al, Ni, Si, Mo, V, Nb, Ta, W, Ge, Te and the Se more than a kind or 2 kinds, and it adds up to 0.1～20 quality %, surplus is made of copper and impurity, be present in particle diameter among precipitate in the alloy and the inclusion and be above precipitate of 1 μ m and inclusion particle diameter, satisfy by the relation shown in following (1) formula with the total number of precipitate and inclusion
logN≤0.4742+17.629×exp(-0.1133×X)…(1)
Wherein, the meaning of N is the total number of the precipitate and the inclusion of per unit area, and unit is individual/mm
2, the meaning of X is the particle diameter of precipitate and inclusion, unit is μ m.
2. an Albatra metal-, it is characterized in that, in quality %, contain from Ti:0.01～5%, any that select among Zr:0.01～5% and Hf:0.01～5%, also contain from Zn, Sn, Ag, Mn, Fe, Co, Al, Ni, Si, Mo, V, Nb, Ta, W, Ge, select more than a kind or 2 kinds among Te and the Se, and it adds up to 0.01～20 quality %, surplus is made of copper and impurity, be present in the above precipitate of particle diameter 1 μ m among precipitate in the alloy and the inclusion and the particle diameter of inclusion, total number with precipitate and inclusion, satisfy by the relation shown in following (1) formula
logN≤0.4742+17.629×exp(-0.1133×X)…(1)
Wherein, the meaning of N is the total number of the precipitate and the inclusion of per unit area, and unit is individual/mm
2, the meaning of X is the particle diameter of precipitate and inclusion, unit is μ m.
3. an Albatra metal-, it is characterized in that, in quality %, contain Cr:0.01～5%, also contain from Zn, Sn, Ag, Mn, Fe, Co, Al, Ni, Si, Mo, V, Nb, Ta, W, Ge, select more than a kind or 2 kinds among Te and the Se, and it adds up to 0.01～20 quality %, surplus is made of copper and impurity, be present in the above precipitate of the about 1 μ m of particle diameter among precipitate in the alloy and the inclusion and the particle diameter of inclusion, total number with precipitate and inclusion, satisfy by the relation shown in following (1) formula
logN≤0.4742+17.629×exp(-0.1133×X)…(1)
Wherein, the meaning of N is the total number of the precipitate and the inclusion of per unit area, and unit is individual/mm
2, the meaning of X is the particle diameter of precipitate and inclusion, unit is μ m.
4. according to each described copper alloy in the claim 1～3, it is characterized in that, also contain select among Mg, Li, Ca and the rare earth element more than a kind or 2 kinds, add up to 0.001～2 quality %, replace the part of copper.
5. according to each described copper alloy in the claim 1～4, it is characterized in that, also contain select among P, B, Bi, Tl, Rb, Cs, Sr, Ba, Tc, Re, Os, Rh, In, Pd, Po, Sb, Au, Ga, S, Cd, As and the Pb more than a kind or 2 kinds, and it adds up to 0.001～3 quality %, replaces the part of copper.
6. according to each described copper alloy in the claim 1～5, it is characterized in that the Be that also contains 0.1～5 quality % replaces the part of copper.
7. according to each described copper alloy in the claim 1～6, it is characterized in that the ratio of the maximum value of the average content in the tiny area of at least a kind of alloying element and the minimum value of average content is more than 1.5.
8. according to each described copper alloy in the claim 1～7, it is characterized in that the crystallization particle diameter is 0.01～35 μ m.
9. the manufacture method of an Albatra metal-; Being present in particle diameter that particle diameter among precipitate in the alloy and the field trash is the above precipitate of 1 μ m and field trash, satisfying by the relation shown in following (1) formula with the total number of precipitate and field trash of this copper alloy; The manufacture method of this copper alloy is characterised in that; Melting has the copper alloy of each described chemical composition from claim 1～6; The slab that casting is obtained; At least the temperature province of the slab temperature to 450 ℃ after being right after casting; With the above cooling velocity cooling of 0.5 ℃/s
logN≤0.4742+17.629×exp(-0.1133×X)…(1)
Wherein, the meaning of N is the total number of the precipitate and the inclusion of per unit area, and unit is individual/mm
2, the meaning of X is the particle diameter of precipitate and inclusion, unit is μ m.
10. the manufacture method of an Albatra metal-, this copper alloy be present in that particle diameter is the above precipitate of 1 μ m and the particle diameter of inclusion among precipitate in the alloy and the inclusion, satisfy by the relation shown in following (1) formula with the total number of precipitate and inclusion, the manufacture method of this copper alloy is characterised in that, melting has the copper alloy of each described chemical constitution in the Accessory Right requirement 1～6, the casting sheet that casting is obtained, at least the temperature province of the casting sheet temperature to 450 ℃ after being right after casting, with the above speed of cooling cooling of 0.5 ℃/s, process in the temperature province below 600 ℃
logN≤0.4742+17.629×exp(-0.1133×X)…(1)
Wherein, the meaning of N is the total number of the precipitate and the inclusion of per unit area, and unit is individual/mm
2, the meaning of X is the particle diameter of precipitate and inclusion, unit is μ m.
11. the manufacture method of an Albatra metal-, this copper alloy be present in that particle diameter is the above precipitate of 1 μ m and the particle diameter of inclusion among precipitate in the alloy and the inclusion, satisfy by the relation shown in following (1) formula with the total number of precipitate and inclusion, the manufacture method of this copper alloy is characterised in that, melting has the copper alloy of each described chemical constitution in the Accessory Right requirement 1～6, the casting sheet that casting is obtained, at least the temperature province of the casting sheet temperature to 450 ℃ after being right after casting, with the above speed of cooling cooling of 0.5 ℃/s, after the temperature province below 600 ℃ is processed, be supplied in the thermal treatment of temperature province maintenance more than 30 seconds at 150～750 ℃
logN≤0.4742+17.629×exp(-0.1133×X)…(1)
Wherein, the meaning of N is the total number of the precipitate and the inclusion of per unit area, and unit is individual/mm
2, the meaning of X is the particle diameter of precipitate and inclusion, unit is μ m.
12. the manufacture method of copper alloy according to claim 11 is characterized in that, repeatedly carries out the processing of the temperature province below 600 ℃ and keeps thermal treatment more than 30 seconds 150～750 ℃ temperature province.
13. the manufacture method according to claim 11 or 13 described copper alloys is characterized in that, after last thermal treatment, carries out the processing of the temperature province below 600 ℃.
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