CN102859016A - Wrought copper alloy, copper alloy part, and process for producing wrought copper alloy - Google Patents
Wrought copper alloy, copper alloy part, and process for producing wrought copper alloy Download PDFInfo
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- CN102859016A CN102859016A CN2010800660251A CN201080066025A CN102859016A CN 102859016 A CN102859016 A CN 102859016A CN 2010800660251 A CN2010800660251 A CN 2010800660251A CN 201080066025 A CN201080066025 A CN 201080066025A CN 102859016 A CN102859016 A CN 102859016A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C9/00—Alloys based on copper
- C22C9/01—Alloys based on copper with aluminium as the next major constituent
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C9/00—Alloys based on copper
- C22C9/10—Alloys based on copper with silicon as the next major constituent
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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Abstract
Provided is a wrought copper alloy which has excellent cuttability and extensibility and is optimal for applications where high strength and/or high electrical conductivity is necessary while alleviating environmental burdens. The wrought copper alloy contains 1.5-7.0 mass% Ni, 0.3-2.3 mass% Si, and 0.02-1.0 mass% S and optionally further contains at least one element selected from a group consisting of Sn, Mn, Co, Zr, Ti, Fe, Cr, Al, P, and Zn in a total amount of 0.05-2.0 mass%, with the remainder comprising Cu and incidental impurities. The wrought copper alloy contains a sulfide dispersed therein which contributes to an improvement in cuttability, the sulfide having an average diameter of 0.1-10 [mu]m and an areal proportion of 0.1-10%. The wrought copper alloy has a tensile strength of 500 MPa or more and an electrical conductivity of 25% IACS or more.
Description
Technical field
The present invention relates to employed metal parts in e-machine, precision optical machinery, the automobile etc., particularly made the copper alloy parts that obtain by machining, further relate to the copper alloy that is suitable for these copper alloy parts and stretch material and manufacture method thereof.
Background technology
Method as making metal parts has the machining such as rotary cut, perforation.Machining be a kind of having special complicated shape parts or require in the manufacturing of parts of high dimensional accuracy effectively working method.In the situation of carrying out machining, machinability usually becomes problem.The projects such as cutting swarf processing, life tools, cutting resistance, face of tool roughness are arranged in the machinability, for improving these projects, need to impose improvement to material.
For copper alloy, for reasons such as intensity height, electroconductibility heat conductivity excellence, corrosion resistance excellent, tone excellences, use it in a large amount of metal partss.The processing of being undertaken by cutting also has enforcement more, purposes such as the water tap that tap water is arranged, valve, gear, ornament is used in brass (Cu-Zn system), bronze (Cu-Sn system), xantal (Cu-Al system), German silver (Cu-Zn-Ni system) and is added with the alloy that forms for the lead that improves machinability.In addition, these purposes all need not high strength or high conductivity.
In the purposes that needs high strength or high conductivity, such as in the purposes such as pin material of coaxial switch, use and in phosphor bronze or beryllium copper, to add the plumbous easy cutting phosphorus bronze (referring to patent documentation 1) that forms, easily cut beryllium copper (referring to patent documentation 2).Utilize the fine-limit work machinery such as NC lathe that these materials are carried out machining, be used for the high parts of reliability such as e-machine purposes.
So, in order to improve the machinability of copper alloy, the general lead that adds.Its reason is that lead solid solution can not occur in copper alloy, thereby can be dispersed in imperceptibly in the material, can become easy in this part at cutting swarf and rupture when machining.But because plumbous can impacting human body or environment, thereby its uses just is restricted, and improves for the requirement that improves the material of machinability in the mode that does not contain lead.As the replacement material that contains plumbous copper alloy, add the copper alloy (with reference to patent documentation 3,4) that bismuth forms in known oriented brass or the bronze.Also known in addition have, in brass, form β phase or the γ phase of copper-zinc based compound or add the κ phase that silicon forms copper-silicon based compound by improving zinc concentration, play a role to improve machinability (patent documentation 5,6) by making these compounds as cutting swarf fracture starting point.In bronze, add in addition in addition sulphur and form sulfide, make its method that plays a role (patent documentation 7), be that known is the method (patent documentation 8) of Precipitation alloy relevant for copper-zirconium system, copper-titanium also in the method that plays a role of cutting swarf fracture starting point making sulfide as cutting swarf fracture starting point thus.
[prior art document]
[patent documentation]
Patent documentation 1: Japanese kokai publication sho 50-066423 communique
Patent documentation 2: Japanese kokai publication sho 52-117244 communique
Patent documentation 3: TOHKEMY 2001-059123 communique
Patent documentation 4: TOHKEMY 2000-336442 communique
Patent documentation 5: TOHKEMY 2000-319737 communique
Patent documentation 6: TOHKEMY 2004-183056 communique
Patent documentation 7: TOHKEMY 2006-152373 communique
Patent documentation 8: TOHKEMY 2001-240923 communique
Patent documentation 9: TOHKEMY 2008-75172 communique
Patent documentation 10: Japanese kokai publication hei 6-212374 communique
Patent documentation 11: Japanese kokai publication hei 7-90520 communique
Summary of the invention
[inventing problem to be solved]
But the technology that each patent documentation is put down in writing has following problem.
In patent documentation 1,2 described technology, as mentioned above, used lead as being used for improving the interpolation element of machinability, worry that it can cause burden to environment.Particularly in the technology that patent documentation 2 is put down in writing, not to replacing as being used for improving the lead that easily cuts the interpolation element of beryllium copper machinability, and it is to understand one of element that environment is impacted that beryllium itself also is construed to, and not only wishes to have the cry of the replacement material that has added plumbous copper alloy but also the replacement material of wishing beryllium copper also to improve gradually.
In addition, in patent documentation 3,4 described technology, when adding bismuth, machinability improves, but is easy to break in the processing, is difficult to especially carry out hot-work.That is, need to seek in addition the improvement of hot workability.The formed compound of alloy by record in the patent documentation 5,6 is the peculiar material of brass system, in fact is difficult to be applicable in other alloy system.Patent documentation 7 is the technology about foundry goods, and this technology is suitable for situation that foundry goods is directly cut, but and unexposed with it as for the technology that obtains the stretching, extension materials such as bar or sheet material (material that forms through plastic working).The intensity of the resulting material of technology of employing patent documentation 8 records is usually lower, such as being inadequate in the high-intensity purposes of needs such as coaxial switch pin material, needs to use other technology.
Above-mentioned patent documentation 1～8 is disclosed to be not to be corson alloy (Cu-Ni-Si series copper alloy), at all can't be as a reference.In TOHKEMY 2008-75172 communique (above-mentioned patent documentation 9), disclose do not add in the situation of other alloying element as far as possible, but can provide the Cu-ni-si-based alloy for electronic material that has improved electric conductivity, intensity, bendability and stress relaxation characteristics concurrently.But not about taking into account disclosing of extensibility and machinability, also do not touch the adjustment of relevant sulphur concentration.Although in Japanese kokai publication hei 6-212374 communique (above-mentioned patent documentation 10), Japanese kokai publication hei 7-90520 communique (above-mentioned patent documentation 11), disclose the corson alloy of considering extensibility, all sulphur concentration be limited in below the 20ppm (0.002%) for this reason.
The present invention proposes in view of such problem, and its problem is to provide an Albatra metal-to stretch material, and its machinability and extensibility be excellent, can alleviate carrying capacity of environment and be best suited in the purposes that needs high strength or high conductivity.The further problem of the present invention is to provide the manufacture method of copper alloy parts and above-mentioned stretching, extension material, and described copper alloy parts obtain by above-mentioned copper alloy stretching, extension material is carried out machining.
[solving the means of problem]
The inventor conducts in-depth research, found that, control with area occupation ratio by the size (mean diameter) to sulfide in the Precipitation type copper alloy of specific composition, the copper alloy that can obtain extensibility (hot cold-workability) and machinability excellence and intensity and excellent electric conductivity stretches material.Find in addition to be used for obtaining composition and the castmethod of above-mentioned sulfide, further found hot workability, cold-workability also composition, tissue, the castmethod of excellence.
The inventor conducts in-depth research in addition, found that, be that the sulfide of 1:1～1:100 is scattered in the matrix by in the matrix of the Precipitation type copper alloy of specific composition, forming sulfide and making in the matrix grain that is present in the cross section parallel with direction of extension more than 40% of this sulfide, make the aspect ratio in the cross section that is parallel to direction of extension, can obtain thus extensibility (hot cold-workability) and machinability copper alloy excellent and intensity and excellent electric conductivity and stretch material.And found to be used for to obtain the composition of above-mentioned sulfide and manufacture method, further found also excellent composition, tissue, manufacture method of hot workability, cold-workability.
The present invention is based on these opinions and finishes.
That is, the invention provides following solution.
(1) one Albatra metal-stretches material, it contains the Si of Ni, the 0.3 quality %～2.3 quality % of 1.5 quality %～7.0 quality %, the S of 0.02 quality %～1.0 quality %, surplus is formed by Cu and inevitable impurity, this copper alloy stretches material and is characterised in that, it is dispersed with sulfide, and the size of this sulfide (mean diameter) is that the area occupation ratio of 0.1 μ m～10 μ m, this sulfide is 0.1%～10%; And the tensile strength that this copper alloy stretches material is that 500MPa is above, electric conductivity is more than the 25%IACS.
(2) stretch material such as (1) described copper alloy, it is characterized in that, it further contains at least a in the group that is comprised of Sn, Mn, Co, Zr, Ti, Fe, Cr, Al, P and Zn of being selected from of counting 0.05 quality %～2.0 quality % with total amount.
(3) stretch material such as (1) or (2) described copper alloy, wherein, above-mentioned sulfide is to be selected from least a in the group that is comprised of Cu-S, Mn-S, Zr-S, Ti-S, Fe-S, Al-S, Cr-S and Zn-S.
(4) one Albatra metal-parts, its each described copper alloy stretching, extension material to (1)～(3) carries out machining and forms.
(5) such as (4) described copper alloy parts, it is used for e-machine parts, structure unit or key element parts.
(6) one Albatra metal-s stretch the manufacture method of material, and it is the manufacture method of each described copper alloy stretching, extension material of (1)～(3), the method is characterized in that the speed of cooling when making casting is 0.1 ℃/second～50 ℃/second.
(7) one Albatra metal-s stretch material, it contains the Si of Ni, the 0.3 quality %～2.3 quality % of 1.5 quality %～7.0 quality %, the S of 0.02 quality %～1.0 quality %, surplus is formed by Cu and inevitable impurity, this copper alloy stretches material and is characterised in that, sulfide is dispersed in the matrix, and the tensile strength that this copper alloy stretches material is that 500MPa is above, electric conductivity is more than the 25%IACS; In the described sulfide, be parallel to that the sulfide of area occupation ratio more than 40% is present in the matrix crystallization in the cross section of direction of extension, the aspect ratio that is parallel in the cross section of direction of extension is 1:1～1:100.
(8) stretch material such as (7) described copper alloy, it is characterized in that this copper alloy stretches material and further contains at least a in the group that is comprised of Sn, Mn, Co, Zr, Ti, Fe, Cr, Al, P and Zn of being selected from of counting 0.05 quality %～2.0 quality % with total amount.
(9) stretch material such as (7) or (8) described copper alloy, wherein, above-mentioned sulfide is selected from more than one in any sulfide of Cu-S, Mn-S, Zr-S, Ti-S, Fe-S, Al-S, Cr-S and Zn-S system.
(10) one Albatra metal-parts, its each described copper alloy stretching, extension material to (7)～(9) carries out machining and forms.
(11) such as (10) described copper alloy parts, it is used for the purposes of the desired strengths such as e-machine parts, structure unit, key element parts, electroconductibility, heat conductivity, wear resistant.
(12) one Albatra metal-s stretch the manufacture method of material, it is the manufacture method that each described copper alloy of (7)～(9) stretches material, this manufacture method is characterised in that: to containing the Ni of 1.5 quality %～7.0 quality %, 0.3 the Si of quality %～2.3 quality %, 0.02 the S of quality %～1.0 quality %, surplus adds man-hour by the copper alloy composition that Cu and inevitable impurity form, implement (a), (b) the arbitrary operation in, impose 0%～95% section shrinkage processing thereafter, make being present in more than 40% in the matrix crystallization of the total area that is dispersed in the sulfide in the matrix in the cross section that is parallel to direction of extension, making aspect ratio in the cross section that is parallel to direction of extension is that the sulfide of 1:1～1:100 is dispersed in the matrix, and the material that so obtains is carried out ageing treatment.
(a) after hot-work, carry out chilling.
(b) after hot-work, repeatedly carry out the thermal treatment of 600 ℃～1000 ℃ of cold working more than 1 time and temperature, before final cold working, imposing solution treatment.
(13) stretch the manufacture method of material such as (12) described copper alloy, it is characterized in that this copper alloy stretches material and further contains at least a in the group that is comprised of Sn, Mn, Co, Zr, Ti, Fe, Cr, Al, P and Zn of being selected from of counting 0.05 quality %～2.0 quality % with total amount.
Herein, so-called " be parallel in the cross section of direction of extension the sulfide of area occupation ratio 40% or more be present in the matrix crystallization interior " refer to, is dispersed in the sulfide in the matrix more than 40% in crystal boundary.In addition, so-called " sulfide that is parallel in the cross section of direction of extension disperses take aspect ratio as 1:1～1:100 " refer to that the aspect ratio that is dispersed in the whole sulfide in the matrix is the scope of 1:1～1:100.Herein, so-called matrix refers in the alloy structure by regional or its set that crystal boundary surrounded, typically is by crystal boundary and surrounds, and exists with any form island adjacent one another are separately.
[effect of invention]
Copper alloy of the present invention stretches intensity and the excellent electric conductivity of material, and does not utilize the carrying capacity of environment materials such as lead or beryllium, machinability and extensibility excellent.For example, in order to prevent the reduction of the desired contact engaging and separating force of connector pin material, can increase to suppressing the reduction of contact engaging and separating force with the beryllium copper equal extent by making tensile strength.The present invention can suppress with the tensile strength more than the 500MPa reduction of contact engaging and separating force with beryllium copper equal extent ground.And in the parts of the e-machine that requires tensile strength or electroconductibility etc., the electric conductivity that copper alloy of the present invention stretches material is more than the 25%IACS, and therefore than beryllium copper, excellent electric conductivity is so be dominant.In addition, copper alloy of the present invention stretches material and makes the parts material of the e-machine that obtains etc. as utilizing machining and suit.Copper alloy parts of the present invention can come precision to make well by machining, and fully have the needed characteristic of parts as e-machine etc.
Above-mentioned and other feature and advantage of the present invention can be more clear and definite according to following record and appended accompanying drawing.
Description of drawings
Fig. 1 is for schematically showing the figure that abreast the copper alloy rod is observed viewed side (a) and cross section (b) with direction of extension.
Fig. 2 has schematically shown and has utilized electron microscope (SEM) and direction of extension abreast the copper alloy rod to be observed viewed section structure, and it is the integral body picture of crystal boundary and sulfide.
Fig. 3 has schematically shown and has utilized electron microscope (SEM) and direction of extension abreast the copper alloy rod to be observed viewed section structure, and it is to have removed the figure shown in the sulfide that is positioned among Fig. 2 on the crystal boundary.
Fig. 4 amplifies the part of Fig. 2 for explanation the figure of the aspect ratio of rear shown sulfide.
Fig. 5 is the side elevational view that schematically shows a kind of shape of the connector pin member (ピ Application) of making among embodiment 1-3, the 2-3.
Fig. 6 is the side elevational view that schematically shows other shape of the connector pin member of making among embodiment 1-3, the 2-3.
Embodiment
Stretch the preferred implementation of material about copper alloy of the present invention, roughly be divided into the 1st embodiment and the 2nd embodiment describes in detail.Wherein, in the 2nd embodiment, the description thereof will be omitted sometimes for the common point with the 1st embodiment.These two embodiments have identical or corresponding specified features, have formed single inventive concept.Need to prove that in this manual, so-called " copper alloy " refers to the material that does not comprise the shape concept, what is called " Cu alloy material " or " copper alloy stretching, extension material " etc. refers to the material that comprises the shape concept.
[the 1st embodiment]
<Ni、Si>
Nickel (Ni) and silicon (Si) in the preferred implementation of the copper alloy stretching, extension material of present embodiment add for following purpose, namely, in metal matrix (dried rhizome of rehmannia, matrix), form Ni-Si precipitate (Ni by control Ni with the content ratio of Si
2Si), carry out thus precipitation strength, the intensity and the electroconductibility that make copper alloy stretch material are improved.This Ni-Si precipitate (Ni
2Si: the precipitate that is used for precipitation strength) do not given play to too large effect in the raising of machinability.
Copper alloy in present embodiment stretches in the preferred implementation of material, is formed with in matrix by the interpolation of sulphur (S) to help the sulfide that machinability improves.This sulfide when carrying out machining cutting swarf fracture starting point and play a role, thereby make cutting swarf slightly produce easily fracture, machinability is improved.In addition, speed of cooling during by the control casting is controlled size (mean diameter) and the area occupation ratio of sulfide, thereby improve the cutting swarf breaking property, further because can not damaging hot workability and cold-workability, thereby can extrude, roll, stretching etc. stretches and process.
Copper alloy in the present embodiment can occur under the state of solid solution or be formed with under the state of Ni-Si precipitate to impose heat or cold working at nickel (Ni) and silicon (Si), but it is usually all relatively poor no matter to stretch processibility under any state, work in-process produce easily break, damaged etc.If in this copper alloy, form sulfide, then stretch processibility and further worsen, be difficult to process.The size of sulfide (mean diameter) can impact stretching processibility with area occupation ratio, thereby in the present embodiment the size (mean diameter) of sulfide is stipulated with area occupation ratio.Thus, the stretching, extension processibility and the machinability that are difficult to have concurrently in the Cu-Ni-Si system are improved simultaneously.
The content of Ni is 1.5 quality %～7.0 quality % (quality %), be preferably 1.7 quality %～6.5 quality %.If Ni amount is very few, then based on little, the undercapacity of the curing amount of separating out of Ni-Si precipitate.If the Ni amount is too much, then because of the superfluous Ni-Si precipitate amount that helps intensity to improve that not only can not increase, but also can form the Ni-Si crystallisate in a large number when the dissolving casting, thereby hot workability and cold-workability (being extensibility) are worsened, thereby not preferred.
At Ni-Si precipitate (Ni
2Si) in the formation, if calculate with quality %, then needing to make Si content is about 1/5～1/3 amount of Ni content.Thus, in the present embodiment, the content of Si is 0.3 quality %～2.3 quality %, be preferably 0.34 quality %～2.2 quality %.
<S>
The copper alloy of present embodiment stretches in the material, and the size (mean diameter) that need to make the sulfide of existence is that the area occupation ratio of 0.1 μ m～10 μ m, sulfide is 0.1%～10%.Therefore, the content of S is 0.02 quality %～1.0 quality %, is preferably 0.03 quality %～0.8 quality %.If very few, then the area occupation ratio of sulfide is little, can't obtain sufficient cutting swarf breaking property.If the content of S is too much, then hot workability and cold-workability (being extensibility) worsen.
In the past, the amount of the S in the corson alloy being restricted to denier is known (above-mentioned patent documentation 10,11).In the present embodiment, it is significantly increased and make other add element and be specified range, preferably carry out under given conditions its processing treatment, stretch material thereby can be made into sulfide at the copper alloy that direction of extension has particular aspect ratio, reach taking into account of machinability and extensibility.
Further, stretch in the material at the copper alloy of present embodiment, can contain one kind or two or more in tin (Sn), manganese (Mn), cobalt (Co), zirconium (Zr), titanium (Ti), iron (Fe), chromium (Cr), aluminium (Al), phosphorus (P), the zinc (Zn).These elements are by solid solution or form the intensity that precipitate improves the Cu-Ni-Si alloy, perhaps improve machinability by forming sulfide.Containing in the situation of these elements, preferably in total amount contain 0.05 quality %～2.0 quality % be selected from Sn, Mn, Co, Zr, Ti, Fe, Cr, Al, P, Zn in one kind or two or more.Content is less than in the situation of 0.05 quality %, and the effect that intensity improves or machinability improves is as good as with the situation that does not contain these elements.In addition, in the situation of content more than 2.0 quality %, not only the effect that improves of intensity and machinability can reach capacity, and electric conductivity also can reduce, thereby is not very wise move.As sulfide composition, Cu-S, Mn-S, Zr-S, Ti-S, Fe-S, Al-S, Cr-S, Zn-S system etc. are arranged, Cu-S is that sulfide is effective especially.The sulfide that further also has inevitable impurity and S.
＜about the regulation of sulfide 〉
As sulfide composition, Cu-S, Mn-S, Zr-S, Ti-S, Fe-S, Al-S, Cr-S, Zn-S etc. are arranged.Sulfide is preferably and is selected from least a in the group that is comprised of Cu-S, Mn-S, Zr-S, Ti-S, Fe-S, Al-S, Cr-S, Zn-S, and Cu-S is effective especially.The sulfide that further also has inevitable impurity and S.Need to prove that herein " Cu-S " means Cu
2The general name of the sulfide that S, CuS etc. are formed by Cu and S, " Mn-S " etc. also is same.
Next, narrate with regulation and the feature of area occupation ratio for the size (mean diameter) as the sulfide of the compound that helps machinability to improve.Sulfide has the slightly effect of fracture of cutting swarf that produces when making machining, improves thus machinability.Yet, if the size of sulfide (mean diameter) can not get larger effect less than 0.1 μ m.And, be the above sulfide of 0.1 μ m even if having size (mean diameter), if total area rate is little, also can't make slightly fracture of cutting swarf.Specifically, if the sulfide of the above size of 0.1 μ m (mean diameter) does not distribute with 0.1%～10% density in area occupation ratio, cutting swarf is fully ruptured.Need to prove, sulfide is softer, therefore be stretched in the longitudinal direction corresponding to hot-work or cold worked degree of finish sometimes, as long as make this moment the size (mean diameter) of sulfide and area occupation ratio satisfy above-mentioned condition perpendicular to the cross section (cross section) of stretching the material length direction.In addition, the size of so-called sulfide (mean diameter) is following value: utilize its cross section of electron microscope observation, the sulfide grain more than 100 is carried out circle convert, its diameter is averaged, with the size of this value as sulfide.The area occupation ratio of so-called sulfide is following value: utilize electron microscope to observe, sulfide number seen in 1 visual field is added up, each sulfide is carried out circle to convert, obtain its diameter and average, obtain area by its mean diameter, then multiply by the quantity of sulfide, obtain the total area of sulfide in per 1 visual field, and divided by the total area in 1 visual field, the value of gained is the area occupation ratio of sulfide.
On the other hand, sulfide makes the hot and cold processibility variation of material.Sulfide is easy to form, make grain-boundary strength to reduce at crystal boundary, if therefore the size (mean diameter) of sulfide is excessive or area occupation ratio is excessive, then can produces when implementing hot-work or cold working and break, and can't use as stretching material.Thereby the size (mean diameter) that need to make sulfide is that 10 μ m are following, to make the area occupation ratio of sulfide be below 10%.
The size of this sulfide (mean diameter) can change along with the speed of cooling in when casting.If speed of cooling is slow, then sulfide can become large; Otherwise if speed of cooling is fast, then sulfide can diminish.Preferred speed of cooling is 0.1 ℃/second～50 ℃/second, more preferably 0.3 ℃/second～40 ℃/second.
＜mechanical property and create conditions
Next, the mechanical property of the stretching, extension of the copper alloy in the preferred implementation of the present invention's the 1st embodiment material is narrated.
The purpose that copper alloy in the present embodiment stretches material is to replace containing plumbous phosphor bronze or beryllium copper, namely replace containing the copper alloy of carrying capacity of environment material, and need to be equality strength with the stretching, extension material of these alloys.Therefore, as the intensity that can not go wrong in the practicality and electroconductibility, need to make tensile strength is that 500MPa is above, electric conductivity is counted more than the 25%IACS with IACS (International Annealed Copper Standard, I.A.C.S.).Copper alloy in the present embodiment is the Precipitation type, as mentioned above, and by forming Ni
2Si, its intensity, electroconductibility are improved, and therefore need to contain the Ni of 1.5 quality %～7.0 quality %, the Si of 0.3 quality %～2.3 quality %.And the temperature during solution treatment in the manufacturing process is preferably 750 ℃～1000 ℃ scope, and the temperature during ageing treatment is preferably 350 ℃～600 ℃ scope.
In the present embodiment, stretch in the manufacture method of material at copper alloy, the speed of cooling when casting except making is regulated in above-mentioned scope the size (mean diameter) of sulfide, and there is no particular restriction.For example, for the area of ingot bar (biscuit or steel billet) cross section, as long as greater than the area that stretches the material cross section.It is the stretching, extension material of Precipitation type copper alloy that the copper alloy of present embodiment stretches material, thereby after the dissolving casting process of copper alloy raw material, must carry out the timeliness heat treatment step at least, except being used for obtaining also can carrying out as required hot procedure, annealing operation, solution treatment operation the operation of copper alloy stretching, extension material.For example, for hot procedure, the copper alloy that the manufacture method such as the heat forged of hot-extrudable, the ingot bar of steel billet or continuous casting all can be made present embodiment stretches material.In addition, also there is no particular restriction for the shape of goods, is preferably the shape that is easy to obtain the copper alloy parts of final form by the cutting process as rear operation.That is, according to the purposes of copper alloy parts, the mode that stretches material with the copper alloy of the specified shapes such as line, rod, bar, plate, pipe is made and is distinguished use and gets final product.For example, the copper alloy parts of final form are in the situation of screw or rivet etc., and what the preferably copper alloy stretched material is shaped as the pole shape.
As the copper alloy parts, can enumerate: the pin (オ ス ピ Application), the pin female (メ ス ピ Application) that use at present the coaxial switch of leaded phosphor bronze or beryllium copper; The bobbin of employed probe and plunger material in IC socket or the battery terminal connector; The e-machine parts of the connector terminals of Sound cable etc.; The hinge of antenna, fastener, bearing, guide rail, resistance welding machine; The structure unit of clock and watch etc. or gear, bearing; Desired strength, electroconductibility, heat conductivity, the wear resistant of key element parts such as the thimble of metal die etc. and so on and the parts of mainly making by machining with the shape of complexity." the copper alloy parts " of present embodiment also can comprise the part utilizing machining and make the copper alloy parts that obtain.
[the 2nd embodiment]
<Ni、Si>
Copper alloy in present embodiment stretches in the material, also Ni is controlled with the content ratio of Si.Its aim is identical with the 1st embodiment.
Copper alloy in present embodiment stretches in the preferred implementation of material, is formed with in matrix by the interpolation of sulphur (S) to help the sulfide that machinability improves.This sulfide when carrying out machining cutting swarf fracture starting point and play a role, thereby make easily slightly fracture of cutting swarf, machinability is improved; It is identical with above-mentioned the 1st embodiment in this.Sulfide forms when casting, but mostly is present in the crystal boundary when forming, and hot workability and cold-workability (being extensibility) are worsened.Therefore, for the sulfide that forms in the ingot bar (biscuit or steel billet), by stretching processing and thermal treatment, make that the sulfide of area occupation ratio more than 40% is present in the matrix crystallization in the cross section that is parallel to direction of extension, so that be that the sulfide of 1:1～1:100, preferred aspect ratio are that the sulfide of 1:1～1:50 is dispersed in the matrix in the cross section that is parallel to direction of extension from the being seen aspect ratio of direction of extension, improve thus the cutting swarf breaking property, further by not damaging the hot and cold processibility, thereby can extrude, roll, processing is stretched in stretching etc.The copper alloy of present embodiment can occur under the state of solid solution or form under the state of Ni-Si precipitate to impose heat or cold working at nickel (Ni) and silicon (Si), but it is usually all relatively poor that it stretches processibility under arbitrary state, work in-process produce easily break, damaged etc.If form sulfide in this copper alloy, then stretching processibility can further worsen, and is difficult to process.The location of sulfide can produce considerable influence to stretching processibility, mostly is present in the crystallization by making sulfide, can make extensibility become good.In the present embodiment, the area occupation ratio that exists in crystal grain for sulfide is stipulated.
The content of Ni is 1.5 quality %～7.0 quality % (quality %), be preferably 1.7 quality %～6.5 quality %.If Ni amount is very few, then based on little, the undercapacity of the curing amount of separating out of Ni-Si precipitate.If the Ni amount too much, then because of the superfluous Ni-Si precipitate amount that helps intensity to improve that not only can not increase, but also can form the Ni-Si crystallisate in a large number when the dissolving casting, thus hot workability and cold-workability (being extensibility) are worsened, thus not preferred.
At Ni-Si precipitate (Ni
2Si) in the formation, if calculate with quality %, then needing to make Si content is about 1/5～1/3 amount of Ni content.Thus, in the present embodiment, the content of Si is 0.3 quality %～2.3 quality %, be preferably 0.34 quality %～2.2 quality %.
<S>
The copper alloy of present embodiment stretches in the material, need to make that area occupation ratio 40% above sulfide is present in the cross section matrix crystallization that is parallel to direction of extension in the formed sulfide, and to make the aspect ratio of the sulfide in the cross section that is parallel to direction of extension be aforementioned proportion.In order to reach this condition, the content that makes S is 0.02 quality %～1.0 quality %, be preferably 0.03 quality %～0.8 quality %.If it is very few, then can not get sufficient cutting swarf breaking property.If the content of S is too much, then hot workability and cold-workability (being extensibility) worsen.The sulfide more than 50% of area occupation ratio in the sulfide that forms and disperse is present in the matrix crystallization.In the present embodiment, also be to contain S above existing common specified amount with above-mentioned positive addition, in this, it is identical with the 1st embodiment.
＜other adds element 〉
Stretch in the material at the copper alloy of present embodiment, can contain one kind or two or more in tin (Sn), manganese (Mn), cobalt (Co), zirconium (Zr), titanium (Ti), iron (Fe), chromium (Cr), aluminium (Al), phosphorus (P), the zinc (Zn).Its effect and preferred content scope etc. are identical with above-mentioned the 1st embodiment.
＜about the regulation of sulfide 〉
Next, for narrating as the regulation and the feature that have ratio and sulfide aspect ratio in the matrix crystallization of sulfide in being parallel to the cross section of direction of extension of the compound that helps to improve machinability.Sulfide has the slightly effect of fracture of cutting swarf that produces when making machining, improves thus machinability.But there is considerable influence the location of sulfide to extensibility (hot workability, cold-workability).The exist ratio of sulfide in matrix grain is the following value that obtains: utilize electron microscope that the cross section that is parallel to direction of extension is observed, the quantity of whole sulfide that statistics is observed in 1 visual field, this each sulfide is carried out circle to convert, obtain its diameter and average, obtain area by this mean diameter, multiply by the sulfide number, try to achieve the total area of the whole sulfide that arrive seen in 1 visual field, afterwards only to adding up with the sulfide number that strides across crystal boundary in the crystal grain, this each sulfide is carried out circle to convert, obtain its diameter and average, obtain area by this mean diameter, multiply by the sulfide number, try to achieve the interior total area with striding across the sulfide of crystal boundary of crystal grain, divided by the total area of the whole sulfide that arrive seen in 1 visual field, the value of gained is that sulfide exists ratio in matrix grain.For this ratio, as long as the interior sulfide with striding across crystal boundary of crystal grain is more than 40%.If below 40%, extensibility variation then.Need to prove that the sulfide area occupation ratio of this moment is in 0.1%～20%, preferably is in 0.1%～10% scope.The area occupation ratio of sulfide is that the sulfide total area that arrives seen in 1 visual field is divided by the resulting value of the total area in 1 visual field.
Sulfide is softer, therefore can the in the longitudinal direction elongation corresponding to hot-work or cold worked degree of finish, and can fracture and be dispersed in the matrix.The aspect ratio of the sulfide that disperses refers to following ratio: utilize electron microscope that this cross section is observed, the length t of direction that will be vertical with direction of extension
1Be made as at 1 o'clock, be parallel to the sulfide length t that direction of extension ground extends
2Ratio (t
2/ t
1).This possibly can't satisfy the S content of regulation when surpassing 1:100, and when machining, cutting swarf can slightly not rupture.Need to prove that sulfide is under direction of extension is not situation for linearity, above-mentioned definition is also unchanged, as shown in Figure 4, obtains the length t of the direction of extension that occupies this area part
2And with the length t of the direction of its quadrature
1, estimate.
The mensuration example of sulfide
Fig. 1 (a) is the front elevation of abreast copper alloy rod 10 being observed with direction of extension R, and Fig. 1 (b) is sectional view, and 10a represents the cross section; It is the figure that schematically shows.
Fig. 2 is the synoptic diagram that carries out abreast the electron microscope observation in cross section with direction of extension, and it shows the crystal boundary 21 and sulfide state of observing in 1 visual field; Among the figure, 21 expression crystal boundaries, 22 expressions are in sulfide, the interior sulfide of 23 expression crystal grain of crystal boundary.Obtain the total area of whole sulfide of in 1 visual field, observing herein.
Next, schematically shown among Fig. 3 and utilized electron microscope (SEM) and direction of extension abreast the copper alloy rod to be observed viewed section structure, it is crystal boundary and the sulfide that is positioned at crystal grain of having removed the sulfide of the crystal boundary that is positioned at Fig. 2.Obtain the total area, the sulfide of trying to achieve seen in 1 visual field and the ratio that is positioned at the sulfide of crystal grain of the sulfide that is positioned at crystal grain shown in this figure.In this case, the area occupation ratio that is positioned at the sulfide of crystal grain is 61%.
The aspect ratio of sulfide refers to, as shown in Figure 4, and with the length t of the direction vertical with direction of extension of sulfide
1Be made as at 1 o'clock, the corresponding sulfide length t that extends abreast with direction of extension
2Ratio (being 13 in the situation of below example among the figure).
＜mechanical properties and create conditions
Next, the mechanical property of the stretching, extension of the copper alloy in the preferred implementation of present embodiment material is narrated.The purpose of the copper alloy in the present embodiment is to replace containing plumbous phosphor bronze or beryllium copper, i.e. replacement contains the copper alloy of carrying capacity of environment material, need to be equality strength with these alloys; This and above-mentioned the 1st embodiment are same.Therefore, in practical the preferable range that requires characteristic (tensile strength, electric conductivity) etc. is same with above-mentioned the 1st embodiment also.
The principal character that the present embodiment copper alloy stretches the manufacture method of material is, the sulfide that is present in a large number crystal boundary during for casting, utilize to stretch processing and thermal treatment, the sulfide more than 40% in area occupation ratio is present in the matrix crystallization, the scope of sulfide take aspect ratio as 1:1～1:100 in the cross section that is parallel to direction of extension is disperseed in the sulfide in the cross section of direction of extension so that be parallel to.
As above-mentioned stretching, extension processing and heat treated preference, can enumerate following example.
(a) after hot-work, carry out chilling, and impose 0%～95% section shrinkage processing of (more preferably 30%～90%), carry out final ageing treatment.
(b) after hot-work, repeatedly carry out the thermal treatment that cold working more than 1 time and temperature are 600 ℃～1000 ℃, imposing solution treatment before final cold working, final ageing treatment is carried out in impose thereafter 0%～95% section shrinkage processing of (more preferably 30%～90%).
Herein, cold working and temperature are that 600 ℃～1000 ℃ thermal treatment is carried out respectively in 1 time the situation, and making cold working is that final cold working, temperature are that 600 ℃～1000 ℃ thermal treatment is solution treatment.
In addition, section shrinkage is processed as cold working, and 0% section shrinkage processing means does not carry out section shrinkage processing.And the temperature during final ageing treatment is preferably 350 ℃～600 ℃, more preferably 400 ℃～550 ℃.
And temperature is that 600 ℃～1000 ℃ heat treated purpose is to improve the processibility that stretches material.The said temperature territory is preferably 800 ℃～1000 ℃, more preferably 900 ℃～1000 ℃.In addition, the heat treated time is preferably 1 hour to 3 hours.And cooling conditions is actually arbitrarily, can be for slow cooling, also can be chilling.The scope that speed of cooling needs only at 0.1 ℃/second～1000 ℃/second is fully.
Consider close to 1:1, the aspect that suitably processes to carry out the control of the shape of sulfide and dispersion state by section shrinkage that from the sulfide aspect ratio that makes the cross section that is parallel to direction of extension the operation that preferably is about to carry out above-mentioned section shrinkage first being processed is hot-work or solution treatment.In this case, the temperature of hot-work or solution treatment is preferably 750 ℃～1000 ℃, more preferably 850 ℃～1000 ℃, more preferably 900 ℃～1000 ℃.
Need to prove, by after just finishing hot-work (hot calender, heat are stretched line, hot-extrudable etc.), carrying out chilling (quenching-in water etc.), can obtain the effect equal with solution treatment at once.
It is the stretching, extension material of Precipitation type copper alloy that the copper alloy of present embodiment stretches material, thereby prerequisite is for suitably adopting at least ageing treatment process after the dissolving casting process of copper alloy raw material; Except being used for obtaining operation that copper alloy stretches material, also can carry out as required the heat treatment step of 600 ℃～1000 ℃ of hot procedures, annealing operation, solution treatment operation, temperature.For example, for hot procedure, copper alloy that any one in the manufacture method such as the heat forged of hot-extrudable, the ingot bar of steel billet or continuous casting all can be made present embodiment stretches material.
In addition, for shape and the copper alloy parts of goods, as its preferable case, can enumerate the situation same with above-mentioned the 1st embodiment.
[embodiment]
Further the present invention is described in detail based on embodiment for the below, but the present invention is not limited thereto.
(embodiment 1)
(embodiment 1-1)
Utilize the high frequency smelting furnace for being dissolved by the copper alloy that forms shown in the table 1-1 alloying constituent, cast each steel billet with 0.5 ℃/second～5 ℃/second of speed of cooling.The diameter that makes steel billet is 200mm.Under 950 ℃ temperature, above-mentioned steel billet is carried out hot-extrudablely, carry out immediately quenching-in water, obtain the pole of diameter 20mm.Next above-mentioned pole is carried out cold stretching, make the pole of diameter 10mm, further under 450 ℃ temperature, carry out 2 hours timeliness thermal treatment.
Stretch material (pole) sample for each copper alloy that so obtains, carry out as follows the investigation of [1] tensile strength, [2] electric conductivity, [3] machinability.The measuring method of each assessment item is as follows.
[1] tensile strength
According to JIS Z 2241,3 copper alloys are stretched material measure, provide its mean value (MPa).
[2] electric conductivity
Adopt four-terminal method, in the thermostatic bath that is controlled to be 20 ℃ (± 1 ℃), each sample is measured by per 2, provide its mean value (%IACS).
[3] machinability
Use general lathe to carry out the segmentation machining of pole external diameter, the diameter of making large diameter part is that the diameter of 9.6mm, small diameter part is the rivet of 8mm, the form of the cutting swarf that observation post produces.With cutting swarf be fractured into below the length 5mm situation as good, with the cutting swarf fracture but its length be below the above 10mm of 5mm situation as can, with the spiral situation of cutting swarf as bad.The situation that can not have problems in the practicality is good and can.In addition, for machining condition, establish rotating speed and be 1010rpm, speed of feed and be per 1 rotation 0.1mm, approach (Qie り Write body generation) be 0.2mm.Cutting tool uses superhard cutter processed, does not use machining oil.
In addition, the size of sulfide (mean diameter) and area occupation ratio are tried to achieve as getting off: for any 3 place's cross sections of the pole sample of diameter 10mm, use scanning electron microscope (SEM) respectively structure observation to be carried out in 3 visuals field, try to achieve thus size (mean diameter) and the area occupation ratio of sulfide.Following the trying to achieve of the size of sulfide (mean diameter): the sulfide more than 100 in per 1 visual field is carried out circle convert, its diameter is average, thus try to achieve the size of sulfide.The area occupation ratio of sulfide is following tries to achieve: the quantity of adding up the sulfide that arrives seen in 1 visual field, and multiply by supposition sulfide and be the area that circle is obtained by mean diameter, try to achieve thus the total area of sulfide in per 1 visual field, divided by the area in 1 visual field, obtain thus the area occupation ratio of sulfide.In addition, sulfide composition is to use the subsidiary energy dispersion type fluorescent x-ray analyzer (EDX) of SEM to investigate.
Among the table 1-1 result has been shown.Among inventive example 1-1～1-25, composition is in the scope of the present invention, and all satisfying tensile strength is that 500MPa is above, electric conductivity is more than the 25%IACS.And the area occupation ratio that the size of sulfide (mean diameter) satisfies 0.1 μ m～10 μ m, sulfide satisfies 0.1%～10%, crack-free in the materials processing, also satisfies machinability.
Comparative example 1-1～1-9 is that composition is in the outer example of the scope of the invention.Among comparative example 1-1 and the 1-3, Ni concentration and Si concentration are low, poor tensile strength.Among the comparative example 1-2, Ni concentration and Si concentration are high, the conduction rate variance.Among the comparative example 1-4, Ni concentration and Si concentration are high, break when cold working.Among the comparative example 1-5, S concentration is low, the area occupation ratio of sulfide is little, and machinability is poor.Among comparative example 1-6 and the 1-7, S concentration is high, the area occupation ratio of sulfide increases, and breaks when hot-work.Among comparative example 1-8 and the 1-9, the total amount of Sn, Mn, Co, Zr, Ti, Fe, Cr, Al, P, Zn surpasses 2.0 quality %, the conduction rate variance.
Conventional example 1-1,1-2 are easy cutting phosphorus bronze and easily cut beryllium copper.The copper alloy of the inventive example stretches material in the situation that does not contain the carrying capacity of environment material such just like the material of conventional example 1-1,1-2, still can obtain the equal above characteristic with conventional example 1-1,1-2.
[table 1-1]
(embodiment 1-2)
Utilize the inventive example 1-6 of table 1-1 and the alloying constituent of inventive example 1-16, (25mm * 25mm * 300mm), the speed of cooling the when preheating temperature by changing mold etc. changes casting is made small-sized ingot bar thus with bench work to use experiment.Resulting ingot bar is carried out hot calender and carries out immediately quenching-in water 950 ℃ temperature, obtain the pole of diameter 20mm.Next above-mentioned pole is carried out cold stretching, make the pole of diameter 10mm, further carry out 2 hours timeliness thermal treatment 450 ℃ temperature.Stretch the sample of material (pole) for each copper alloy that so obtains, carry out the investigation of [1] tensile strength, [2] electric conductivity, [3] machinability according to the method identical with above-described embodiment 1-1, the size of sulfide (mean diameter) is obtained too as stated above with area occupation ratio.The results are shown among the table 1-2.
[table 1-2]
Inventive example 1-26～1-29 and the inventive example 1-6 of table 1-2 are that same alloy composition, inventive example 1-30～1-33 and inventive example 1-16 are the same alloy composition, the example that changes within the scope of the invention for speed of cooling.If speed of cooling increases, then the size of sulfide (mean diameter) is tended to reduce, but all within the scope of the invention; Obtained excellent machinability.Comparative example 1-10,1-11 and the inventive example 1-6 of table 1-2 are that same alloy composition, comparative example 1-12,1-13 and inventive example 1-16 are the same alloy composition, for speed of cooling is in the outer example of the scope of the invention.In the slow situation of speed of cooling (comparative example 1-10 and 1-12), it is large that the size of sulfide (mean diameter) becomes, and breaks in cold or hot-work.In the fast situation of speed of cooling (comparative example 1-11 and 1-13), the size of sulfide (mean diameter) is less than 0.1 μ m, and machinability is bad.
(embodiment 1-3)
Utilize the inventive example 1-6 of table 1-1 and the alloying constituent of inventive example 1-16, the pole of the diameter 10mm that is obtained by the method through embodiment 1-1 is made
With
Pole.For these poles, come respectively 1000 of construction drawing 5 and connector pin members as shown in Figure 6 with the NC lathe.Its result carries out man-hour that adds of parts, and cutting swarf is around being attached on the processing component, and does not produce dimensional change because of the instrument abrasion.In addition, for machining condition, in external diameter processing, rotating speed is made as 3000rpm, speed of feed is made as per 1 rotation 0.02mm; In Drilling operation, rotating speed is made as 2500rpm, speed of feed is made as per 1 rotation 0.03mm, uses machining oil.Among Fig. 5,50 expression connector pin members, 51 expression slits.Among Fig. 6, the connector pin member of 60 expression another way, 61 expression slits, 62 expression tapered portion.
For the connector pin member of Fig. 5 shape, carry out the evaluation as the necessary plug of pin material characteristic.Evaluation method is as follows: will
Pin gauge be inserted in the pin member after the processing and measure contact engaging and separating force (initial value T0), then this pin member is carried out extracting out for 500 times repeatedly and inserts, again measure afterwards contact engaging and separating force (T1), obtain the ratio T1/T0 with respect to initial value.The reduction of the large then contact engaging and separating force of T1/T0 is little, can say functional as the connector pin member.5 pin members are estimated, obtained mean value.For comparing, also estimate for the conventional example 1-1 of table 1-1 and the material of 1-2.The results are shown among the table 1-3.
By table 1-3 as can be known, the inventive example be the connector pin member of excellence, has demonstrated equal plug with the easy cutting beryllium copper of conventional example 1-2.The plug of the easy cutting phosphorus bronze of conventional example 1-1 is inferior to the inventive example, may loose contact when life-time service.
[table 1-3]
| Title | The evaluation (T1/T0) of plug property |
| Inventive example 1-6 | 0.86 |
| Inventive example 1-16 | 0.80 |
| Conventional example 1-1 | 0.53 |
| Conventional example 1-2 | 0.85 |
(embodiment 2)
(embodiment 2-1)
The copper alloy that forms shown in the alloying constituent of use table 2-1 similarly obtains sample with above-described embodiment 1-1.The measuring method of each characteristic and condition are same with above-described embodiment 1-1 also.
Be parallel to sulfide in the cross section of direction of extension and be present in following the trying to achieve of area occupation ratio in the matrix crystallization: the cross section that is parallel to direction of extension for any 3 places of diameter 10mm pole sample, use scanning electron microscope (SEM) respectively structure observation to be carried out in 3 visuals field, try to achieve thus above-mentioned area occupation ratio.Add up whole sulfide numbers of observing in 1 visual field, this each sulfide is carried out circle to convert, obtain its diameter, average, try to achieve area by its mean diameter, multiply by the sulfide number, obtain the total area of whole sulfide of in 1 visual field, seeing, afterwards only to adding up with the sulfide number that strides across crystal boundary in the crystal grain, this each sulfide is carried out circle to convert, obtain its diameter, average, obtain area by its mean diameter, multiply by the sulfide number, obtain the interior total area with striding across the sulfide of crystal boundary of crystal grain, divided by whole sulfide total areas of in 1 visual field, seeing, thereby try to achieve described area occupation ratio.In addition, for sulfide composition, use the subsidiary energy dispersion type fluorescent x-ray analyzer (EDX) of SEM to investigate.In addition, although not shown in the table, in the stretching, extension material of the inventive example, the aspect ratio that is parallel in the cross section of direction of extension all is in the scope of 1:1～1:100, and the area occupation ratio that stretches the sulfide in the cross section of material satisfies 0.1%～10%.
Among the table 2-1 result has been shown.Among inventive example 2-1～2-25, composition all satisfies tensile strength and is that 500MPa is above, electric conductivity is more than the 25%IACS within the scope of the invention.And, being parallel to being present in more than 40% in the matrix crystallization of sulfide in the cross section of direction of extension, material work in-process crack-free, machinability also are met.
Comparative example 2-1～2-9 is that alloy composition is in the outer example of the scope of the invention.Among comparative example 2-1 and the 2-3, Ni concentration and Si concentration are excessively low, thereby have only obtained the inadequate alloy of tensile strength.Among the comparative example 2-2, Ni concentration and Si excessive concentration, conduction rate variance.Among the comparative example 2-4, Ni concentration and Si excessive concentration are broken when cold working.Among the comparative example 2-5, S concentration is low, although be parallel to being present in more than 40% in the matrix crystallization of sulfide in the cross section of direction of extension, machinability is poor.Among comparative example 2-6 and the 2-7, S concentration is high, but does not make being present in more than 40% in the matrix crystallization of sulfide in the cross section that is parallel to direction of extension, breaks when hot-work.Among comparative example 2-8 and the 2-9, the total amount of Sn, Mn, Co, Zr, Ti, Fe, Cr, Al, P, Zn surpasses 2.0 quality %, the conduction rate variance.
Conventional example 2-1,2-2 are easy cutting phosphorus bronze and easily cut beryllium copper.The copper alloy of the inventive example stretches material in the situation that does not contain the carrying capacity of environment material such just like the material of conventional example 2-1,2-2, still can obtain the equal above characteristic with conventional example 2-1,2-2.
[table 2-1]
* break in the crystal grain of material, the area occupation ratio of sulfide
(embodiment 2-2)
Utilize the copper alloy of inventive example 2-1,2-6,2-16 and the comparative example 2-5 composition of high frequency smelting furnace his-and-hers watches 2-1 to dissolve, with each steel billet of 1 ℃ of/second casting of speed of cooling diameter 300mm.Under 950 ℃ of temperature, above-mentioned steel billet is carried out hot-extrudablely, carry out immediately quenching-in water, obtain the pole of diameter 30mm.Thereafter by cold stretching processing, being machined to diameter is 20mm, carries out solution treatment under 950 ℃ of temperature, obtains the pole of diameter 20mm.
This pole is carried out section shrinkage processing, make respectively the pole of diameter 20mm (section shrinkage processing 0%), diameter 16mm (section shrinkage processing 36.0%), diameter 10mm (section shrinkage processing 75.0%), diameter 4.5mm (section shrinkage processing 94.9%), diameter 3.5mm (section shrinkage processing 96.9%).Further, for diameter 20mm, 500 ℃ of ageing treatment of carrying out 2 hours; For diameter 16mm, 480 ℃ of ageing treatment of carrying out 2 hours; For diameter 10mm, 450 ℃ of ageing treatment of carrying out 2 hours; For diameter 4.5mm and 3.6mm, 430 ℃ of ageing treatment of carrying out 2 hours.Stretch the sample of material (pole) for each copper alloy that so obtains, carry out the investigation of [1] tensile strength, [2] electric conductivity according to the method identical with above-described embodiment 1, carry out by the following method the research of [3] machinability.
[3] machinability
Use general lathe that the material of each diameter is carried out the outer processing of cutting, make the pole of diameter 3mm, carry out the segmentation machining of pole external diameter.Form to the cutting swarf that produces is observed, with cutting swarf fragment into below the length 5mm situation as good, with the cutting swarf fracture but its length be below the above 10mm of 5mm situation as can, with the spiral situation of cutting swarf as bad.The situation that can not have problems in the practicality is good and can.In addition, for machining condition, rotating speed is made as 1010rpm, speed of feed is made as per 1 rotation 0.1mm, approach is made as 0.2mm.Cutting tool uses superhard cutter processed, does not use machining oil.
Be parallel to sulfide in the cross section of direction of extension and be present in following the trying to achieve of area occupation ratio in the matrix crystallization: the cross section that is parallel to direction of extension for any 3 places of the pole sample of diameter 20,16,10,4.5,3.5mm, use scanning electron microscope (SEM) respectively structure observation to be carried out in 3 visuals field, try to achieve this area occupation ratio by aforesaid method.In addition, for the aspect ratio of sulfide, will by above-mentioned electron microscope observation to the vertical direction of direction of extension of sulfide be made as 1, recently try to achieve this aspect ratio by the length of the sulfide that extends abreast with direction of extension.
[table 2-2]
The inventive example 2-26 of table 2-2～2-37 and inventive example 2-1,2-6,2-16 are the same alloy composition, for having implemented the example of the section shrinkage processing in the scope of the invention.All satisfying tensile strength is that 500MPa is above, electric conductivity is more than the 25%IACS.And, the sulfide that is present in the matrix crystallization more than 40%, is parallel in the cross section of direction of extension that is parallel to sulfide in the cross section of direction of extension disperses take aspect ratio as 1:1～1:100, and the material work in-process breaks, machinability also is met.
Comparative example 2-10～2-12 is the alloy composition in the scope of the invention, but the section shrinkage working modulus is outside the scope of the present invention, breaks when cold working.Comparative example 2-13～2-16 and comparative example 2-5 are the same alloy composition.Comparative example 2-13～2-15 is the section shrinkage processing in the scope of the invention, and S concentration is low, although thereby be parallel to being present in more than 40% in the matrix crystallization of sulfide in the cross section of direction of extension, but machinability is poor.Comparative example 2-16 is the outer section shrinkage processing of the scope of the invention, is parallel to being present in more than 40% in the matrix crystallization of sulfide in the cross section of direction of extension, does not break; Surpass 1:100 with aspect ratio and disperse but be parallel to sulfide in the cross section of direction of extension, machinability is poor.
(embodiment 2-3)
Utilize the inventive example 2-6 of table 2-1 and the alloy composition of inventive example 2-16, similarly the plug of connector is estimated with embodiment 1-3.By the table 2-3 that its result is shown as can be known, the inventive example is excellent connector pin member, has demonstrated equal plug with the easy cutting beryllium copper of conventional example 2-2.The plug of the easy cutting phosphorus bronze of conventional example 2-1 is inferior to the inventive example.
[table 2-3]
| Title | Ratio with respect to the contact engaging and separating force initial value |
| Inventive example 2-6 | 0.86 |
| Inventive example 2-16 | 0.80 |
| Conventional example 2-1 | 0.53 |
| Conventional example 2-2 | 0.85 |
Adopt this embodiment to describe the present invention, but should think, as long as the applicant there is no and specifies, then the present application is not limited to illustrated any thin section, should pay not violating under the condition of the spiritual and scope of the invention shown in the claim and carry out wide in range explanation.
The application advocates to carry out the right of priority of the Japanese Patent Application 2010-210201 that patent submits to, on June 24th, 2010 carry out carrying out in Japan in the right of priority of the Japanese Patent Application 2010-143420 that patent submits to and on April 7th, 2010 the Japanese Patent Application 2010-88228 that patent submits in Japan right of priority based on carrying out the right of priority of the Japanese Patent Application 2010-280946 that patent submits to, on September 17th, 2010 in Japan on December 16th, 2010 in Japan, the application is inserted into the part of its content as the record of this specification sheets among the application with reference to the content of above-mentioned each patent application.
[explanation of symbol]
10 copper alloys rod
The 10 ' copper alloy that cuts off in direction of extension is excellent
The cross section that 10a is parallel with direction of extension
The R direction of extension
21 crystal boundaries
22 are in the sulfide of crystal boundary
Sulfide in 23 crystal grain
The length of 24 directions vertical with the direction of extension of sulfide
The length of 25 directions parallel with the direction of extension of sulfide
50,60 connector pin members
51,61 slits
62 tapered portion
Claims (13)
1. an Albatra metal-stretches material, it contains the Si of Ni, the 0.3 quality %～2.3 quality % of 1.5 quality %～7.0 quality %, the S of 0.02 quality %～1.0 quality %, surplus is formed by Cu and inevitable impurity, this copper alloy stretches material and is characterised in that, it is dispersed with sulfide, and the mean diameter of this sulfide is that the area occupation ratio of 0.1 μ m～10 μ m, this sulfide is 0.1%～10%; And the tensile strength that described copper alloy stretches material is that 500MPa is above, electric conductivity is more than the 25%IACS.
2. an Albatra metal-stretches material, it contains the Si of Ni, the 0.3 quality %～2.3 quality % of 1.5 quality %～7.0 quality %, the S of 0.02 quality %～1.0 quality %, further contain at least a in the group that is formed by Sn, Mn, Co, Zr, Ti, Fe, Cr, Al, P and Zn of being selected from of counting 0.05 quality %～2.0 quality % with total amount, surplus is formed by Cu and inevitable impurity, this copper alloy stretches material and is characterised in that, it is dispersed with sulfide, and the mean diameter of this sulfide is that the area occupation ratio of 0.1 μ m～10 μ m, this sulfide is 0.1%～10%; And the tensile strength that described copper alloy stretches material is that 500MPa is above, electric conductivity is more than the 25%IACS.
3. stretch material such as claim 1 or copper alloy claimed in claim 2, wherein, described sulfide is to be selected from least a in the group that is comprised of Cu-S, Mn-S, Zr-S, Ti-S, Fe-S, Al-S, Cr-S and Zn-S.
4. Albatra metal-parts, its each described copper alloy to claim 1～3 stretch material to carry out machining and forms.
5. copper alloy parts as claimed in claim 4, it is used for e-machine parts, structure unit or key element parts.
6. an Albatra metal-stretches the manufacture method of material, and it is the manufacture method of each described copper alloy stretching, extension material of claim 1～3, and this manufacture method is characterised in that the speed of cooling when making casting is 0.1 ℃/second～50 ℃/second.
7. an Albatra metal-stretches material, it contains the Ni of 1.5 quality %～7.0 quality %, 0.3 the Si of quality %～2.3 quality %, 0.02 the S of quality %～1.0 quality %, surplus is formed by Cu and inevitable impurity, this copper alloy stretches material and is characterised in that, sulfide is dispersed in the matrix, and the tensile strength that described copper alloy stretches material is more than the 500MPa, electric conductivity is more than the 25%IACS, in the described sulfide, be parallel in the cross section of direction of extension, the area occupation ratio of the sulfide that exists in the matrix crystallization is more than 40%, be parallel in the cross section of direction of extension, the aspect ratio in the cross section of described sulfide is 1:1～1:100.
8. copper alloy as claimed in claim 7 stretches material, it is characterized in that this copper alloy stretches material and further contains at least a in the group that is comprised of Sn, Mn, Co, Zr, Ti, Fe, Cr, Al, P and Zn of being selected from of counting 0.05 quality %～2.0 quality % with total amount.
9. stretch materials such as claim 7 or 8 described copper alloys, wherein, described sulfide is to be selected from any sulfide of Cu-S, Mn-S, Zr-S, Ti-S, Fe-S, Al-S, Cr-S and Zn-S system more than one.
10. Albatra metal-parts, its each described copper alloy to claim 7～9 stretch material to carry out machining and forms.
11. copper alloy parts as claimed in claim 10, it is used for the purposes of the desired strengths such as e-machine parts, structure unit, key element parts, electroconductibility, heat conductivity, wear resistant.
12. an Albatra metal-stretches the manufacture method of material, it is the manufacture method of each described copper alloy stretching, extension material of claim 7～9, this manufacture method is characterised in that: to containing the Ni of 1.5 quality %～7.0 quality %, 0.3 the Si of quality %～2.3 quality %, 0.02 the S of quality %～1.0 quality %, surplus adds man-hour by the copper alloy composition that Cu and inevitable impurity form, implement following (a), (b) the arbitrary operation in, impose 0%～95% section shrinkage processing thereafter, make being present in more than 40% in the matrix crystallization of the sulfide total area that is dispersed in the cross section that is parallel to direction of extension in the matrix, the matrix that is dispersed with sulfide is carried out ageing treatment, and the aspect ratio of the sulfide that disperses in being parallel to the cross section of direction of extension is 1:1～1:100; Described operation (a), (b) are:
(a) after hot-work, carry out chilling;
(b) after hot-work, repeatedly carry out the thermal treatment of 600 ℃～1000 ℃ of cold working more than 1 time and temperature, before final cold working, imposing solution treatment.
13. copper alloy as claimed in claim 12 stretches the manufacture method of material, it is characterized in that this copper alloy stretches material and further contains at least a in the group that is comprised of Sn, Mn, Co, Zr, Ti, Fe, Cr, Al, P and Zn of being selected from of counting 0.05 quality %～2.0 quality % with total amount.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010088228 | 2010-04-07 | ||
| JP2010-088228 | 2010-04-07 | ||
| JP2010-143420 | 2010-06-24 | ||
| JP2010143420A JP4630387B1 (en) | 2010-04-07 | 2010-06-24 | Copper alloy wrought material, copper alloy parts, and method for producing copper alloy wrought material |
| JP2010210201 | 2010-09-17 | ||
| JP2010-210201 | 2010-09-17 | ||
| JP2010280946 | 2010-12-16 | ||
| JP2010-280946 | 2010-12-16 | ||
| PCT/JP2010/073451 WO2011125264A1 (en) | 2010-04-07 | 2010-12-24 | Wrought copper alloy, copper alloy part, and process for producing wrought copper alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102859016A true CN102859016A (en) | 2013-01-02 |
| CN102859016B CN102859016B (en) | 2015-04-08 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201080066025.1A Expired - Fee Related CN102859016B (en) | 2010-04-07 | 2010-12-24 | Wrought copper alloy, copper alloy part, and process for producing wrought copper alloy |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20130028784A1 (en) |
| EP (1) | EP2557187A1 (en) |
| KR (1) | KR101294508B1 (en) |
| CN (1) | CN102859016B (en) |
| TW (1) | TW201134959A (en) |
| WO (1) | WO2011125264A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106103756A (en) * | 2014-03-25 | 2016-11-09 | 古河电气工业株式会社 | The manufacture method of copper alloy plate, connector and copper alloy plate |
| CN108368565A (en) * | 2016-05-16 | 2018-08-03 | 古河电气工业株式会社 | Copper series alloy wire rod |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013099242A1 (en) * | 2011-12-28 | 2013-07-04 | Yazaki Corporation | Ultrafine conductor material, ultrafine conductor, method for preparing ultrafine conductor, and ultrafine electrical wire |
| JP5802150B2 (en) * | 2012-02-24 | 2015-10-28 | 株式会社神戸製鋼所 | Copper alloy |
| DE102013005158A1 (en) * | 2013-03-26 | 2014-10-02 | Kme Germany Gmbh & Co. Kg | copper alloy |
| DE102013014500A1 (en) * | 2013-09-02 | 2015-03-05 | Kme Germany Gmbh & Co. Kg | copper alloy |
| DE102014207331B4 (en) * | 2014-04-16 | 2017-01-26 | Federal-Mogul Wiesbaden Gmbh | Lead-free CuNi2Si bearing material with the addition of a break-breaking metal |
| DE102015001293B4 (en) * | 2015-02-02 | 2022-11-17 | Isabellenhütte Heusler Gmbh & Co. Kg | power rail arrangement |
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- 2010-12-24 CN CN201080066025.1A patent/CN102859016B/en not_active Expired - Fee Related
- 2010-12-24 EP EP10849504A patent/EP2557187A1/en not_active Withdrawn
- 2010-12-24 KR KR1020117031351A patent/KR101294508B1/en active IP Right Grant
- 2010-12-27 TW TW099145993A patent/TW201134959A/en not_active IP Right Cessation
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| CN1764775A (en) * | 2003-03-31 | 2006-04-26 | 日立金属株式会社 | Piston for internal combustion engine |
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| CN108368565A (en) * | 2016-05-16 | 2018-08-03 | 古河电气工业株式会社 | Copper series alloy wire rod |
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| CN108368565B (en) * | 2016-05-16 | 2020-07-31 | 古河电气工业株式会社 | Copper alloy wire |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102859016B (en) | 2015-04-08 |
| US20130028784A1 (en) | 2013-01-31 |
| TWI365226B (en) | 2012-06-01 |
| EP2557187A1 (en) | 2013-02-13 |
| WO2011125264A1 (en) | 2011-10-13 |
| TW201134959A (en) | 2011-10-16 |
| KR101294508B1 (en) | 2013-08-07 |
| KR20120089566A (en) | 2012-08-13 |
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