CN101791638A - The manufacture method of Cu-Ag alloy wire and Cu-Ag alloy wire - Google Patents
The manufacture method of Cu-Ag alloy wire and Cu-Ag alloy wire Download PDFInfo
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Abstract
The invention provides a kind of can high production rate ground make the Cu-Ag alloy wire manufacture method of superfine Cu-Ag alloy wire and superfine Cu-Ag alloy wire, this manufacture method is carried out wire drawing to the blank of the Ag that contains 0.5～15.0 quality %, makes the superfine wire that finish line directly is less than or equal to 0.05mm.Carry out the removal of superficial layer for being in stage midway that reaches the wire drawing before the finish line footpath and the wire rod that line footpath φ is less than or equal to 1.0mm.The removal of this superficial layer such as following carrying out promptly, when 1/2 of the line footpath φ of the wire rod before superficial layer is removed is made as r, make the surface layer thickness t that removes satisfy t/r 〉=0.02.The superfine Cu-Ag alloy wire that obtains can suitably be applied to the center conductor of coaxial cable maybe with the stranded twisted wire that forms of this Cu-Ag alloy wire.
Description
Technical field
The present invention relates to a kind of superfine wire that constitutes by the Cu-Ag alloy, with this superfine wire as the twisted wire of line material, with these superfine wires or twisted wire manufacture method as the coaxial cable and the above-mentioned superfine wire of conductor.
Background technology
In recent years, be accompanied by the miniaturization of various electronic equipments, light-weighted demand, the thin footpathization (patent documentation 1) of conductors such as the employed coaxial cable of expectation electronic equipment.As superfine conductor material, a kind of conductance height, Cu-Ag alloy wire (patent documentation 2) that strength ratio copper is high have been proposed.
For the employed superfine wire of superfine conductor, normally wire drawing produces by blanks such as founding materials are carried out.In manufacturing process, the foreign matter of constituent material that comes employed crucible or mold the comfortable operation till being melted to casting and connect their chute etc. is sneaked in the blank.For sneaking into of this foreign matter, even use highly purified raw material also to be difficult to avoid.In addition, in wire-drawing process, might produce defective, perhaps sneak into foreign matter in blank surface in blank surface.The existence of above-mentioned foreign matter or blemish becomes the main cause that breaks when making superfine wire, the productivity ratio of superfine wire is reduced.Disclose a kind of method in patent documentation 1, it is difficult to produce in order to make to break, and utilizes chemolysis when the extremely finish line of the line footpath of the line material after Wire Drawing undergauge footpath.
But, under prior art, can make the superfine Cu-Ag alloy wire that is less than or equal to 0.05mm in high production rate ground hardly.
Patent documentation 1 discloses the technology of the copper cash material of wire drawing to the 20 μ m (0.02mm) of line footpath being implemented electrochemical dissolution.But, under existing method,, break so often produce during the 0.02mm of line footpath in wire drawing because wire drawing is difficult to being less than or equal to the method itself that 0.05mm makes the superfine wire of long size, be difficult to obtain the copper cash material of length size.In addition, because the absolute value of foreign matter diameter is constant, so under the situation of the superficial layer of the wire rod of removing line footpath 0.02mm, because the foreign matter diameter becomes big with respect to the ratio in line footpath, so if removal amount is less, then be difficult to foreign matter is removed fully, if increase removal amount for foreign matter is removed fully, then discarded amount (the wire rod weight before the wire rod weight/removal superficial layer behind the removal superficial layer) increases.As described in patent documentation 1, if with the line material undergauge of line footpath 20 μ m to line footpath 14 μ m, then yield rate is approximately 50%, has discarded half.Because being somebody's turn to do discarded amount be to comprise the part that is machined to the expense that is produced till the 0.02mm, the problem that cause yield rate deterioration, cost to raise so exist this part is discarded.
Patent documentation 1: the spy opens the 2002-140935 communique
Patent documentation 2: the spy opens the 2001-040439 communique
Summary of the invention
The present invention In view of the foregoing proposes, and one of its purpose is to provide a kind of manufacture method of Cu-Ag alloy wire, the broken string when it can reduce wire drawing, thus the Cu-Ag alloy wire that line directly is less than or equal to 0.05mm is made on high production rate ground.In addition, other purpose of the present invention is to provide a kind of high conductivity and high-intensity superfine Cu-Ag alloy wire and this superfine wire is carried out the stranded twisted wire that forms and with this superfine wire or the twisted wire coaxial cable as center conductor.
The inventor finds, promptly, be less than or equal in manufacturing under the situation of the very thin like this Cu-Ag alloy wire of 0.05mm, by wire rod to the specific dimensions in stage midway of being in wire drawing, remove the superficial layer of specified quantitative, thereby the broken string in the time of can reducing wire drawing effectively, can high production rate ground make the superfine wire of desired size.
Based on above-mentioned discovery, in the preparation method of Cu-Ag alloy wire of the present invention, specific superficial layer is removed.Specifically, the manufacture method of Cu-Ag alloy wire of the present invention is that the blank that contains the Ag that is less than or equal to 15.0 quality % more than or equal to 0.5 quality % is implemented Wire Drawing and made finish line and directly be the method for the superfine wire that is less than or equal to 0.05mm, and this method has following superficial layer and removes operation.
Superficial layer is removed operation: the wire rod that is in the stage midway that reaches the wire drawing before the finish line footpath is carried out the removal of superficial layer.This superficial layer is removed operation and is had the fine rule manufacturing procedure especially, and in this operation, the superficial layer than thin wire that line footpath φ is less than or equal to 1.0mm is removed.And the removal of the superficial layer in this fine rule manufacturing procedure is carried out in the following manner, that is, when 1/2 of the line of the wire rod before will removing superficial layer footpath φ is made as r, make the surface layer thickness t that removes satisfy t/r 〉=0.02.
Can consider and to carry out peeling and blank after removing foreign matter or blemish is used for wire drawing to the blank before the wire drawing.But, even the inventor finds to carry out as mentioned above peeling in upstream process, also can under the situation that is less than or equal to 0.05mm, the particularly very thin Cu-Ag alloy wire about 0.025mm by wire drawing manufacturing, often produce broken string, be difficult to make continuously superfine wire.That is, even, also can only remove foreign matter or defective on the outmost surface that is present in blank owing to carry out peeling in the upstream, thus might make the foreign matter or the defective that are present in blank inside appear at face side owing to wire drawing thereafter, thus broken string produced.In addition,, also can perhaps produce defective, thereby might produce broken string, be difficult to make continuously superfine wire by sneaking into new foreign matter midway in wire drawing even carry out peeling in the upstream.On the other hand,, after wire drawing, remove superficial layer in the operation in (be about to become finish line footpath before) promptly downstream, then cause aforesaid yield rate to reduce easily and the cost rising if described according to citing document 1.Relative therewith, if the inventor finds to carry out the removal of superficial layer after becoming the thin footpath that is less than or equal to 1.0mm, then be difficult to produce broken string, even the very thin wire rod about 0.025mm also can make continuously because the broken string number of times reduces and can boost productivity.Thus, in manufacture method of the present invention, carry out the removal of superficial layer at the thin footpath wire rod in the stage midway that is in wire drawing.
Manufacture method of the present invention with said structure when manufacturing is less than or equal to the superfine Cu-Ag alloy wire of 0.05mm, is difficult to produce broken string, can carry out wire drawing continuously.Thus, manufacturing method according to the invention can be made the superfine wire rod of long size, and productivity ratio is good.
The blank that is used for wire drawing for example can use implements blank after cold rolling to founding materials.In order to reduce the foreign matter that contains in this blank, preferred higher raw material Cu and the raw material A g of purity for example uses Cu and Ag more than or equal to four nine (purity 99.99%).
Addition to raw material A g is adjusted, so that the content of the Ag in the superfine wire that obtains is 0.5～15.0 quality %.If the content of Ag surpasses 15.0 quality %, even working modulus (contraction percentage of area) or intermediate heat-treatment when then adjusting wire drawing, also can't obtain regulation conductance as described later, if be lower than 0.5 quality %, even working modulus or intermediate heat-treatment when then adjusting wire drawing also can't obtain prescribed strength as described later.
In manufacture method of the present invention, till reaching finish line footpath, carry out the Wire Drawing (particularly cold drawn silk) of multi-pass.Can adjust the wire rod of drawing condition with characteristics such as the line footpath that obtains having expectation and hot strengths.Especially, if the working modulus of the cold drawn silk processing of at first carrying out more than or equal to 70%, then later Wire Drawing is just carried out with the working modulus of stipulating easily.
Under the situation of the Wire Drawing of carrying out multi-pass, if halfway the stage carry out intermediate heat-treatment, then can remove before this intermediate heat-treatment the processing strain that imports wire rod, be easy to carry out later Wire Drawing.In addition, by utilizing intermediate heat-treatment Ag is separated out, and it is fibrous to utilize later Wire Drawing that the Ag precipitate is formed, thereby can improves the intensity of superfine wire.The condition of intermediate heat-treatment can exemplify out heating-up temperature: 350～500 ℃ (preferred 400～450 ℃), retention time: 0.5～10 hour.
In manufacture method of the present invention, the superficial layer in the preferred at least fine rule manufacturing procedure is removed and is undertaken by chemical treatment or electrochemical treatments.The wire rod of the object of superficial layer is removed in conduct in the fine rule manufacturing procedure, because its line footpath φ is more carefully for being less than or equal to 1.0mm, if, then be difficult to make the center of wire rod and the center-aligned of nib, cause productivity ratio to reduce so utilize the peeling mould that when peeling, uses usually.On the other hand, chemical treatment or electrochemical treatments not only can be implemented simply to the wire rod in any one line footpath, and because the surface after handling is very level and smooth, the defective etc. that becomes disconnect reason is difficult to exist, so when the wire rod after handling is continued to implement Wire Drawing, be difficult to broken string, stringiness is good.Can enumerate electrobrightening etc. as representational processing.Also can utilize known processing.In the fine rule manufacturing procedure, remove the wire rod of superficial layer, as long as line directly is less than or equal to φ 1.0mm, if but because the line footpath is too small, then the discarded amount of removing from wire rod increases, cause manufacturing cost to increase, so preferred line footpath is more than or equal to φ 0.2mm.
In addition, because there is limit in the minimizing by the foreign matter that utilizes highly purified raw material to make to contain in the founding materials, studies so the amount of the foreign matter that the inventor is contained from founding materials just can be allowed the viewpoint of the founding materials of using as superfine wire for which kind of degree.Its result, the part of founding materials got make sample, concentration to the foreign matter that contained is measured, as long as the amount of finding to have more than or equal to the foreign matter of certain diameter is less than or equal to setting, just can obtains and causes the relevant considerably less founding materials of foreign matter that breaks.And, find that because this founding materials is difficult to broken string when wire drawing so can make superfine wire in high production rate ground, this founding materials can be cast by specified conditions and produce.
In addition, discovery is less than or equal under the situation of the so very thin Cu-Ag alloy wire of 0.05mm in manufacturing, by on the basis of using the less founding materials of the foreign matter relevant with causing above-mentioned broken string, wire rod to the specific dimensions in stage midway of being in wire drawing, remove the superficial layer of specified quantitative, thereby the broken string in the time of can reducing wire drawing effectively, can high production rate ground make the superfine wire of desired size.
Based on above-mentioned discovery, use specific founding materials in the manufacture method of Cu-Ag alloy wire of the present invention, and carry out the removal of specific superficial layer.Specifically, the manufacture method of Cu-Ag alloy wire of the present invention is that the founding materials that contains the Ag that is less than or equal to 15.0 quality % more than or equal to 0.5 quality % is implemented Wire Drawing, thereby make the method that finish line directly is less than or equal to the superfine wire of 0.05mm, it has following casting process and superficial layer is removed operation.
(1) casting process: ready raw material Cu and raw material A g are melted by the crucible that is made of highly purified carbon, this mixed molten liquid is kept making impurity be separated to the surface of mixed molten liquid more than or equal to 30 minutes under more than or equal to the liquidus point temperature of the mixture of Cu and Ag.Then, utilize the mold that is made of highly purified carbon, the mixed molten liquid that use has separated behind the above-mentioned impurity is made founding materials.
(2) superficial layer is removed operation: as mentioned above, the wire rod that is in the stage midway that reaches the wire drawing before the finish line footpath is carried out the removal of superficial layer.This superficial layer is removed operation and is had the fine rule manufacturing procedure especially, in this operation, removes the superficial layer than thin wire that line footpath φ is less than or equal to 1.0mm.And the removal of the superficial layer in this fine rule manufacturing procedure is carried out in the following manner, that is, when 1/2 of the line of the wire rod before will removing superficial layer footpath φ is made as r, make the surface layer thickness t that removes satisfy t/r 〉=0.02.
On the basis of described Wire Drawing, have the manufacture method of the present invention of above-mentioned formation, when manufacturing is less than or equal to the superfine Cu-Ag alloy wire of 0.05mm, be difficult to produce broken string, can carry out wire drawing continuously.Therefore, method constructed in accordance can be made the superfine wire rod of long size, and productivity ratio is good.
In above-mentioned casting process, particularly importantly be used to make impurity to be separated to the retention time on the surface of mixed molten liquid.If this retention time is shorter than 30 minutes, then separate impurities is insufficient, and the foreign matter that contains in the founding materials also increases.Especially, be that founding materials contains with higher probability and causes the foreign matter that broken string is relevant, by utilizing such founding materials, is easy to generate broken string when wire drawing under 0～20 minute the situation in the retention time.As long as retention time does not have special requirement more than or equal to 30 minutes to the upper limit, if but consider productivity ratio, then preferably be less than or equal to 10 hours.
By above-mentioned casting process, can obtain and the less founding materials of foreign matter that causes that broken string is relevant.Specifically, after the part utilization acid of founding materials is dissolved, utilize the filter of aperture 0.2 μ m to filter, the Al amount and the Si amount that contain in the residue thing by the filter recovery are less than or equal to 1 quality ppm with respect to dissolved founding materials separately.That is, Al compound and the Si compound above 0.2 μ m is considerably less in this founding materials.Because it is less to become the thick foreign matter of disrumpent feelings principal element when wire drawing, so by utilizing this founding materials, the broken string in the time of can reducing wire drawing effectively.In addition, surpass under the situation of 1 quality ppm in Al amount and Si amount, preferably make founding materials again, the founding materials that above-mentioned foreign matter is less is used for wire drawing.
In addition, in order to reduce the foreign matter that contains in the founding materials, utilize the crucible and the mold that constitute by highly purified carbon.Specifically, preferably use impurity level to be less than or equal to 20 quality ppm, be more preferably less than or equal the crucible and the mold of the carbon system of 5 quality ppm.In addition, preferably use higher raw material Cu of purity and raw material A g, for example more than or equal to the raw material of four nine (purity 99.99%).
The removal ratio t/r that makes superficial layer in the above-mentioned fine rule manufacturing procedure is more than or equal to 0.02, is preferably greater than or equals 0.08.In addition,, then, defective and foreign matter can be removed fully, the generation of broken string can be reduced because the removal amount of superficial layer increases if comprise the fine rule manufacturing procedure in the interior removal of carrying out repeatedly superficial layer.Repeatedly carrying out under the situation that superficial layer removes, the total of the removal ratio t/r in preferably handling is carried out the removal of superficial layer more than or equal to 0.08 mode with each, more preferably greater than or equal 0.12.But, if since the excessive then yield rate of removal amount worsen, so t/r add up on be limited to about 0.20.In addition, the thickness t of superficial layer is meant from the distance radially of the surface material along the line of wire rod.In addition, for the section shape of wire rod, representational is circular.
The Cu-Ag alloy wire that utilizes manufacture method of the present invention to make also can have coating.By forming coating, except the corrosion resistance that improves the Cu-Ag alloy wire, can improve the connection between wire rod or the connectivity when wire rod is connected with other parts.Coating can enumerate from Au, Au alloy, Ag, Ag alloy, Sn, Sn alloy, Ni and Ni alloy, select more than or equal to a kind.This coating can form in any period carry out the superficial layer removal by the fine rule manufacturing procedure after.That is, the coating operation can be carried out after last wire drawing finishes, also can the wire drawing after the fine rule manufacturing procedure midway (between passage) carry out.Remove superficial layer wire rod afterwards, because surface smoothing and cleaning, so form coating easily.
The Cu-Ag alloy wire of the present invention that utilizes the manufacture method of the invention described above to obtain contains the Ag that is less than or equal to 15.0 quality % more than or equal to 0.5 quality %, remainder is made of Cu and unavoidable impurities, preferred Al amount and Si amount are less, are less than or equal to 1 quality ppm separately.For Cu-Ag alloy wire of the present invention because the content of blemish and foreign matter is considerably less, so for example continue to implement under the situation of Wire Drawing or will many Cu-Ag alloy wire stranded and form under the situation of twisted wire, be difficult to produce and break.In addition, under the situation as the center conductor of coaxial cable, when using, coaxial cable is difficult to produce problems such as broken string with Cu-Ag alloy wire or its twisted wire.
In the invention described above manufacture method, owing to when wire drawing, be difficult to produce broken string, so can obtain superfine Cu-Ag alloy wire of the present invention.Specifically, can make line directly for being less than or equal to 0.05mm.By continuing to implement Wire Drawing, can make line directly be 0.01mm (10 μ m)～0.03mm (30 μ m).
In the invention described above manufacture method,, can obtain high-intensity Cu-Ag alloy wire of the present invention by adding Ag or utilizing work hardening that Wire Drawing causes etc.Special preferred tensile strength is less than or equal to 1600MPa more than or equal to 800MPa.Cu-Ag alloy wire of the present invention with above-mentioned hot strength is difficult to fracture when for example being wound into coiled type or stranded many Cu-Ag alloy wires.Working modulus (contraction percentage of area) in the time of can be to the content of Ag or wire drawing, intermediate heat-treatment condition etc. are adjusted, so that hot strength and conductance described later become desired value.
In containing the manufacture method of the present invention of above-mentioned casting process, the work hardening that causes by Wire Drawing or make above-mentioned Ag precipitate form fibrous effect etc. can obtain high-intensity Cu-Ag alloy wire of the present invention.Special preferred tensile strength is less than or equal to 1600MPa more than or equal to 800MPa.Cu-Ag alloy wire of the present invention with this hot strength is difficult to fracture when for example being wound into coiled type or stranded many Cu-Ag alloy wire.Working modulus (contraction percentage of area) in the time of can be to the content of Ag or wire drawing, intermediate heat-treatment condition etc. are adjusted, so that hot strength and conductance described later become desired value.
More than, the preferred conductance of Cu-Ag alloy wire of the present invention is more than or equal to 65%IACS, be preferably greater than especially or equal 70%IACS, more preferably greater than or equal 80%IACS.The Cu-Ag alloy wire of the present invention of this superfine and high-strength high-conductivity can suitably be applied to the conductor material of various electric equipments.
The manufacture method of Cu-Ag alloy wire according to the present invention can be made the superfine Cu-Ag alloy wire that line directly is less than or equal to 0.05mm continuously, and the productivity ratio of Cu-Ag alloy wire is good.In addition, the Cu-Ag alloy wire that obtains by this manufacture method or the twisted wire of this Cu-Ag alloy wire have high strength and high conductivity, can suitably be applied to the conductor of coaxial cable etc.
The specific embodiment
Manufacturing is investigated stringiness by the many superfine wires that the Cu-Ag alloy constitutes.
(sample 1～4 and Comparative Examples I are to the making of the blank of II)
Prepare cathode copper as raw material Cu, silver granuel (Ag) is as raw material A g.Ready cathode copper is carried out vacuum fusion in continuous casting apparatus.After cathode copper melts fully, be replaced into argon gas in the chamber with continuous casting apparatus, ready above-mentioned silver granuel is put in the crucible melted, the mixed molten liquid that obtains after Cu and the Ag fusing is cast and made founding materials (diameter 22mm).In addition, the addition of silver granuel is adjusted, so that the content of Ag in mixed molten liquid is 0.6 quality % (sample 1～3, I, II) or 5.0 quality % (only sample 4).
Cold rolling to the founding materials enforcement that obtains, after the wire rod that is processed as about diameter 9.5mm, remove superficial layer by the peeling mould, obtain the round line of line footpath 8mm.The round line (blank) that obtains is implemented the cold drawn silk processing of multi-pass, obtain the wire rod of finish line footpath 0.025mm (sample 1～3, I, II) or 0.04mm (only sample 4).In Wire Drawing, used the mould of American Wire Gage specification (AWG specification).In addition, for each sample, all directly formed Ag coating on the wire rod of 0.3mm in stage midway that is in wire drawing and line.
(making of the blank of sample 5～8 and Comparative Example II I to IV)
Prepare purity more than or equal to 99.99% cathode copper as raw material Cu, purity more than or equal to 99.99% silver granuel (Ag) as raw material A g.Ready above-mentioned cathode copper is being carried out pickling, removal is attached to after the lip-deep foreign matter of cathode copper, cathode copper after the pickling and above-mentioned silver granuel are dropped in the high purity carbon system crucible, in continuous casting apparatus, carry out vacuum fusion, make the mixed molten liquid that Cu and Ag fusing forms.In addition, the addition of silver granuel is adjusted, so that the Ag content in the mixed molten liquid is 0.6 quality %.
At above-mentioned mixed molten liquid, after having added silver granuel, under more than or equal to the liquidus point temperature of the mixture of Cu and Ag, kept 30 minutes, make the impurity that comprises foreign matter be separated to the surface of the mixed molten liquid in the above-mentioned crucible.
Make the impurity after separating, using high purity carbon system mold to make the round line (blank) of outlet footpath 8.0mm.Al in resulting founding materials amount and Si amount are measured., take out the 200g founding materials here, be dissolved in the aqueous solution that contains more than or equal to 6.4mol nitric acid, the filter of this soln using aperture 0.2 μ m is filtered, use filter to reclaim the residue thing.The residue thing that reclaims is carried out drying in platinum system crucible, after filter is carried out ashing (ashing), add flux and carry out fusion and form glassy mass.The glassy mass that obtains is dissolved in contains in the aqueous solution of hydrochloric acid.Implement in dust free room (clean booth) from the operation that founding materials is dissolved to till glassy mass dissolves.In addition, induce coupled plasma (ICP) emission spectrographic analysis, thereby Si amount and Al amount are carried out quantitatively by the solution after glassy mass is dissolved.Its result, Si amount: 0.1 quality ppm, Al amount: 0.3 quality ppm, any amount all is less than or equal to 1 quality ppm.In addition, the amount of the founding materials that uses in the mensuration of Si amount and Al amount is just enough about as 100g～200g.
The founding materials that obtains is implemented the cold drawn silk processing of multi-pass, obtain the wire rod of finish line footpath 0.021mm.In Wire Drawing, use the mould of American Wire Gage specification (AWG specification).In addition, for each sample, all directly implement intermediate heat-treatment (400 ℃ * 8 hours) for the wire rod of 2.6mm to stage midway that is in wire drawing and line.In addition, for each sample, all directly be formation Ag coating on the wire rod of 0.3mm in stage midway that is in wire drawing and line.
(sample 1)
For sample 1, in the stage midway that is in wire drawing, line footpath φ be 0.9mm (≤1.0mm) time, wire rod is implemented electrobrightening, remove superficial layer.Electrobrightening is to use phosphate aqueous solution, current density: 40A/dm at electrolyte
2, dip time: 4.5min, temperature: carry out under 30 ℃ the condition.The surface layer thickness t that removes is t=0.040mm.If 1/2 of linear diameter φ is made as r, r=φ * (1/2)=0.9 * (1/2)=0.45 then, t/r ≒ 0.089 (〉=0.02).
(sample 2)
For sample 2, in the stage midway that is in wire drawing, line footpath φ
1For 2.6mm (＞1.0mm) time, wire rod is implemented chemical polishing, remove superficial layer.Chemical polishing is to use the disulfate aqueous solution, dip time: 150min, temperature: carry out under 30 ℃ the condition at polishing fluid.The thickness t of the superficial layer of removing
1Be t
1=0.15mm.If with line footpath φ
11/2 be made as r
1, r then
1=1.30, t
1/ r
1≒ 0.115.In addition, for this sample 2, in the stage midway that is in wire drawing, line footpath φ
2For 0.9mm (≤1.0mm) time, wire rod is implemented chemical polishing same as described above, remove superficial layer.By changing the thickness t that dip time changes the superficial layer of removal
2, make t
2=0.010mm.If with line footpath φ
21/2 be made as r
2, r then
2=0.45, t
2/ r
2≒ 0.022 (〉=0.02).T during 2 subsurface layers are removed
1/ r
1And t
2/ r
2Add up to 0.115+0.022=0.137 (〉=0.08).
(sample 3)
For sample 3, when being 0.9mm, wire rod is implemented the chemical polishing identical with sample 2, removal superficial layer with the online in the same manner footpath φ of sample 1.By changing the thickness t that dip time changes the superficial layer of removal
3, make t
3=0.020mm.If 1/2 of line footpath φ is made as r, then r=0.45, t
3/ r ≒ 0.044 (〉=0.02).
(sample 4)
Sample 4 is to make sample (Ag:5.0 quality %) after the Ag content with respect to sample 2.This sample 4 and sample 2 in the same manner, (t when online footpath φ is 2.6mm
1/ r
1≒ 0.115) and (t during 0.9mm
2/ r
2≒ 0.022), carry out 2 subsurface layers and remove (t
1/ r
1And t
2/ r
2Total: 0.137).In addition, the finish line of this sample 4 directly is 0.04mm.
Comparative Examples (sample I)
Sample I does not carry out the removal of superficial layer in the stage midway of wire drawing, and only forms the sample of coating on wire rod at above-mentioned blank.
Comparative Examples (sample II)
For sample II, in the stage midway that is in wire drawing, line footpath φ
1For 2.6mm (＞1.0mm) time, wire rod is implemented the chemical polishing identical with sample 2, removal superficial layer.The surface layer thickness t that removes
IBe t
I=0.15mm.If 1/2 of line footpath φ is made as r
I, r then
I=1.30, t
I/ r
I≒ 0.115.Carry out the removal of superficial layer when in addition, this sample II does not have online footpath φ for 0.9mm.
(sample 5)
For sample 5, in the stage midway that is in wire drawing, line footpath φ be 0.9mm (≤1.0mm) time, wire rod is implemented electrobrightening, remove superficial layer.Electrobrightening is to use phosphate aqueous solution, current density: 40A/dm at electrolyte
2, dip time: 6.8min, temperature: carry out under 30 ℃ the condition.The surface layer thickness t that removes is t=0.06mm.If 1/2 of line footpath φ is made as r, r=φ * (1/2)=0.9 * (1/2)=0.45 then, t/r ≒ 0.133 (〉=0.02).
(sample 6)
For sample 6, in the stage midway that is in wire drawing, line footpath φ
1For 2.6mm (＞1.0mm) time, wire rod is implemented to implement chemical polishing after the above-mentioned intermediate heat-treatment, remove superficial layer.Chemical polishing is to use the disulfate aqueous solution, dip time: 150min, temperature: carry out under 30 ℃ the condition at polishing fluid.The surface layer thickness t that removes
1Be t
1=0.15mm.If with line footpath φ
11/2 be made as r
1, r then
1=1.30, t
1/ r
1≒ 0.115.In addition, for this sample 6, in the stage midway that is in wire drawing, line footpath φ
2For 0.9mm (≤1.0mm) time, wire rod is implemented chemical polishing same as described above, remove superficial layer.Change the surface layer thickness t of removal by changing dip time
2, make t
2=0.01mm.If with line footpath φ
21/2 be made as r
2, r then
2=0.45, t
2/ r
2≒ 0.022 (〉=0.02).T during 2 subsurface layers are removed
1/ r
1And t
2/ r
2Add up to 0.115+0.022=0.137 (〉=0.08).
(sample 7)
For sample 7, when being 0.9mm, wire rod is implemented the electrobrightening identical with sample 1, removal superficial layer with the online in the same manner footpath φ of sample 5.Change the surface layer thickness t of removal by changing dip time
3, make t
3=0.04mm.If 1/2 of line footpath φ is made as r, then r=0.45, t
3/ r ≒ 0.089 (〉=0.02).
(sample 8)
For sample 8, when being 2.6mm, online footpath φ do not carry out the removal of superficial layer, when online footpath φ is 0.9mm, wire rod is implemented the chemical polishing identical with sample 6, removal superficial layer.Change the surface layer thickness t of removal by changing dip time
4, make t
4=0.02mm.If 1/2 of line footpath φ is made as r, then r=0.45, t
4/ r ≒ 0.044 (〉=0.02).
Comparative Examples: (sample III)
For sample III, in the stage midway that is in wire drawing, line footpath φ
IFor 2.6mm (＞1.0mm) time, wire rod is implemented after the above-mentioned intermediate heat-treatment, implement the chemical polishing identical, the removal superficial layer with sample 6.The surface layer thickness t that removes
IBe t
I=0.15mm.If 1/2 of line footpath φ is made as r
I, r then
I=1.30, t
I/ r
I≒ 0.115.Carry out the removal of superficial layer when in addition, this sample I does not have online footpath φ for 0.9mm.
Comparative Examples: (sample IV)
Sample IV be not wire drawing midway the stage carry out the removal of superficial layer, and only wire rod is implemented the sample of above-mentioned intermediate heat-treatment and coating.
(sample 1～4 and Comparative Examples I are to the evaluation of the stringiness of II)
At each sample, investigate for the stringiness with extremely finish line footpath 0.025mm of the blank wire drawing of line footpath 8mm or 0.04mm the time.Its result is shown in the table 1.Stringiness is estimated by following manner,, above-mentioned blank is prepared 20kg respectively that is, during till the whole wire drawings end of 20kg the broken string number of times that produces is measured, according to 20kg is estimated divided by the value (kg/ time) of this broken string number of times.
(sample 1～4 and Comparative Examples I are to the characteristic of the Cu-Ag alloy wire of II)
In addition, at the sample 1～4, I, the II that obtain, measure hot strength (MPa) and conductance (%IACS).Its result is also shown in the table 1.
[table 1]
| Sample 1 | Sample 2 | Sample 3 | Sample 4 | Comparative sample I | Comparative sample II | |
| Ag measures (quality %) | ??0.6 | ?0.6 | ??0.6 | ?5.0 | ??0.6 | ??0.6 |
| Finish line footpath (mm) | ??0.025 | ?0.025 | ??0.025 | ?0.04 | ??0.025 | ??0.025 |
| Remove superficial layer | ??φ＝0.9??t＝0.040 | ?φ＝2.6，t＝0.15?φ＝0.9，t＝0.010 | ??φ＝0.9??t＝0.020 | ?φ＝2.6，t＝0.15?φ＝0.9，t＝0.010 | Do not have | ??φ＝2.6??t＝0.15 |
| T/r adds up to | ??0.089 | ?0.137 | ??0.044 | ?0.137 | ??- | ??0.115 |
| Stringiness | 2.0kg/ it is inferior | 3.3kg/ it is inferior | 1.8kg/ it is inferior | 10kg/ time | 0.8kg/ it is inferior | 0.8kg/ it is inferior |
| Hot strength | ??910MPa | ?906MPa | ??904MPa | ?1204MPa | ??918MPa | ??917MPa |
| Conductance | ??85％IACS | ?85％IACS | ??85％IACS | ?70％IACS | ??85％IACS | ??85％IACS |
As shown in table 1, the wire rod that line directly is less than or equal to 1.0mm is removed the superficial layer of specified quantitative and the sample 1～4 that obtains as can be known, and their stringiness is all higher, even make line footpath 0.025mm or the so superfine wire rod of 0.04mm, also is difficult to broken string.Be difficult to produce broken string under the situation of online especially footpath 0.04mm, we can say that the effect that the removal by above-mentioned superficial layer obtains is fine.In addition, remove, then be difficult to broken string more if repeatedly carry out superficial layer as can be known.
(evaluation of the stringiness of the Cu-Ag alloy wire of sample 5～8 and Comparative Example II I to IV)
At each sample, for the blank wire drawing of line footpath 8mm the stringiness during to finish line footpath 0.021mm investigate.Its result is shown in the table 2.Stringiness is estimated by following manner,, above-mentioned founding materials is prepared 20kg respectively that is, during till the whole wire drawings end of 20kg the broken string number of times that produces is measured, according to 20kg is estimated divided by the value (kg/ time) of this broken string number of times.
(characteristic of the Cu-Ag alloy wire of sample 5～8 and Comparative Example II I to IV)
In addition, at the sample 5～8 that obtains, measure hot strength (MPa) and conductance (%IACS).Its result is also shown in the table 2.
[table 2]
| Sample 5 | Sample 6 | Sample 7 | Sample 8 | Comparative sample III | Comparative sample IV | |
| Remove superficial layer | ??φ＝0.9??t＝0.06 | ??φ＝2.6，t＝0.15??φ＝0.9，t＝0.01 | ??φ＝0.9??t＝0.04 | ??φ＝0.9??t＝0.02 | ?φ＝2.6?t＝0.15 | Do not have |
| T/r adds up to | ??0.133 | ??0.137 | ??0.089 | ??0.044 | ?0.115 | ??- |
| Stringiness | 1.5kg/ it is inferior | 2.8kg/ it is inferior | 1.4kg/ it is inferior | 1.1kg/ it is inferior | 0.5kg/ it is inferior | 0.4kg/ it is inferior |
| Hot strength | ??950MPa | ??945MPa | ??953MPa | ??955MPa | ?- | ??- |
| Conductance | ??85％IACS | ??85％IACS | ??85％IACS | ??85％IACS | ?- | ??- |
As shown in table 2, use as can be known mixed molten liquid is kept more than or equal to 30 minutes latter made founding materialses under more than or equal to the liquidus point temperature of the mixture of Cu and Ag, and the sample 5～8 that the superficial layer of specified quantitative obtains is removed for the wire rod that is less than or equal to 1.0mm in line footpath, their stringiness is all higher, even make the line footpath less than the so superfine wire rod of 0.025mm, also be difficult to broken string.Especially, if repeatedly carry out the removal of superficial layer as can be known, then be difficult to broken string more.In addition, even use the less founding materials of foreign matter as can be known, if but certain line wire rod is not directly carried out the removal of superficial layer, then under the situation of making so very thin wire rod, also can often produce broken string less than 0.025mm.
In addition, the hot strength of the sample 1～8 that obtains as can be known is all bigger, and conductance is also higher.At the wire rod of preparing 7 above-mentioned samples 1～4 respectively, when making 7 strands of stranded twisted wires, can not can produce broken string and waiting and make twisted wire.In addition, when the twisted wire that will obtain is made coaxial cable as center conductor, can make without a doubt.Therefore, Cu-Ag alloy wire of the present invention fully has the desired characteristic of using of conductors such as distribution in various electric equipments, can suitably be applied to above-mentioned conductor.
In addition, above-mentioned embodiment can suitably change under the situation that does not break away from purport of the present invention, is not limited to said structure.For example, can suitably change content, the superficial layer of Ag the removal ratio, carry out line footpath that superficial layer removes, finish line footpath etc.
The manufacture method of Cu-Ag alloy wire of the present invention can suitably be applied to the manufacturing that line directly is less than or equal to the so superfine wire rod of 0.05mm.Cu-Ag alloy wire of the present invention and twisted wire can suitably be applied to the conductor of automobile or employed coaxial cable of the present invention such as electronic unit, industrial robot.
Claims (10)
1. the manufacture method of a Cu-Ag alloy wire, it implements Wire Drawing to the blank that contains the Ag that is less than or equal to 15.0 quality % more than or equal to 0.5 quality %, thereby makes the superfine wire that finish line directly is less than or equal to 0.05mm,
The manufacture method of this Cu-Ag alloy wire is characterised in that,
Have superficial layer and remove operation, in this operation,, remove the superficial layer of wire rod at the wire rod that is in the stage midway that reaches the wire drawing before the described finish line footpath,
Described superficial layer is removed operation and is had the fine rule manufacturing procedure, in this operation, removes the superficial layer than thin wire that line footpath φ is less than or equal to 1.0mm,
The removal of the superficial layer in the described fine rule manufacturing procedure is carried out in the following manner, that is, when 1/2 of the line of the wire rod before will removing superficial layer footpath φ is made as r, make the surface layer thickness t that removes satisfy t/r 〉=0.02.
2. the manufacture method of Cu-Ag alloy wire as claimed in claim 1 is characterized in that,
Has casting process, in this operation, ready raw material Cu and raw material A g are melted by the crucible that is made of highly purified carbon, this mixed molten liquid is being kept more than or equal to 30 minutes under more than or equal to the liquidus point temperature of the mixture of Cu and Ag, and after making impurity be separated to the surface of mixed molten liquid, use the mold that constitutes by highly purified carbon to make described blank.
3. the manufacture method of Cu-Ag alloy wire as claimed in claim 1 or 2 is characterized in that,
Have repeatedly described superficial layer and remove operation, carry out the removal of superficial layer with the total of the t/r in each operation more than or equal to 0.08 mode.
4. the manufacture method of Cu-Ag alloy wire as claimed in claim 1 or 2 is characterized in that,
Have the coating operation, in this operation, form coating on surface through the wire rod after the described fine rule manufacturing procedure.
5. a Cu-Ag alloy wire is characterized in that,
Manufacture method by the described Cu-Ag alloy wire of claim 1 is made,
Contain the Ag that is less than or equal to 15.0 quality % more than or equal to 0.5 quality %, remainder is made of Cu and unavoidable impurities,
Line directly is less than or equal to 0.05mm.
6. a Cu-Ag alloy wire is characterized in that,
Manufacture method by the described Cu-Ag alloy wire of claim 2 is made,
Contain the Ag that is less than or equal to 15.0 quality % more than or equal to 0.5 quality %, remainder is formed by Cu and unavoidable impurities,
Line directly is less than or equal to 0.05mm.
7. as claim 5 or 6 described Cu-Ag alloy wires, it is characterized in that,
Hot strength is less than or equal to 1600MPa more than or equal to 800MPa.
8. as claim 5 or 6 described Cu-Ag alloy wires, it is characterized in that,
Form coating on the surface,
Described coating is by forming more than or equal to a kind of material of selecting from Au, Au alloy, Ag, Ag alloy, Sn, Sn alloy, Ni and Ni alloy.
9. a Cu-Ag alloy twisted wire is characterized in that,
Claim 5 or 6 described Cu-Ag alloy wires are carried out stranded forming as the line material.
10. a coaxial cable is characterized in that,
Carry out the stranded Cu-Ag alloy twisted wire that forms as center conductor with claim 5 or 6 described Cu-Ag alloy wires or with this Cu-Ag alloy wire as the line material.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009018750A JP5344151B2 (en) | 2009-01-29 | 2009-01-29 | Method for producing Cu-Ag alloy wire and Cu-Ag alloy wire |
| JP2009-018749 | 2009-01-29 | ||
| JP2009018749A JP5344150B2 (en) | 2009-01-29 | 2009-01-29 | Method for producing Cu-Ag alloy wire and Cu-Ag alloy wire |
| JP2009-018750 | 2009-01-29 |
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| CN101791638A true CN101791638A (en) | 2010-08-04 |
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| CN103098146A (en) * | 2010-09-17 | 2013-05-08 | 住友电气工业株式会社 | Coaxial cable |
| CN103572184A (en) * | 2013-10-17 | 2014-02-12 | 河南科技大学 | Preparation method of high-strength silver-copper alloy material |
| CN103572184B (en) * | 2013-10-17 | 2015-07-22 | 河南科技大学 | Preparation method of high-strength silver-copper alloy material |
| CN110373567A (en) * | 2014-04-14 | 2019-10-25 | 株式会社自动网络技术研究所 | Copper alloy wire, copper-alloy stranded conductor and electric wire for automobiles |
| CN104064248A (en) * | 2014-06-13 | 2014-09-24 | 安徽省宁国天成电工有限公司 | Annealed circular copper wire plated with nickel |
| CN105624460A (en) * | 2015-12-29 | 2016-06-01 | 刘雷 | High-conductivity and high-tenacity copper alloy cable conductor and preparation method thereof |
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