EP0023362B2 - Verfahren zur Herstellung einer elektrisch leitfähigen Kupferlegierung - Google Patents
Verfahren zur Herstellung einer elektrisch leitfähigen Kupferlegierung Download PDFInfo
- Publication number
- EP0023362B2 EP0023362B2 EP19800104479 EP80104479A EP0023362B2 EP 0023362 B2 EP0023362 B2 EP 0023362B2 EP 19800104479 EP19800104479 EP 19800104479 EP 80104479 A EP80104479 A EP 80104479A EP 0023362 B2 EP0023362 B2 EP 0023362B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- copper
- alloy
- copper alloy
- zirconium
- chrome
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000956 alloy Substances 0.000 title claims description 39
- 229910000881 Cu alloy Inorganic materials 0.000 title claims description 30
- 238000000034 method Methods 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000010949 copper Substances 0.000 claims description 39
- 229910052802 copper Inorganic materials 0.000 claims description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 28
- 229910052726 zirconium Inorganic materials 0.000 claims description 20
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 17
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052732 germanium Inorganic materials 0.000 claims description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 238000005482 strain hardening Methods 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000005275 alloying Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 description 29
- 238000002844 melting Methods 0.000 description 16
- 230000008018 melting Effects 0.000 description 16
- 239000000243 solution Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 238000004881 precipitation hardening Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- XTYUEDCPRIMJNG-UHFFFAOYSA-N copper zirconium Chemical compound [Cu].[Zr] XTYUEDCPRIMJNG-UHFFFAOYSA-N 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- -1 and the rest Chemical compound 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910001610 cryolite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000003763 resistance to breakage Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
-
- 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
Definitions
- the present invention relates to a method for manufacturing high electrically conductive, precipitation hardenable copper alloy wire material having both high electrical conductivity and mechanical strength.
- GB-A-1 030 427 describes a copper alloy material comprising 0,01-0,15% Zr, the balance being high purity copper and having high electrical conductivity and mechanical strength at elevated temperatures as well as high thermal conductivity of 91.1 IACS or better, fine recrystallized grain size of less than 0,020 millimeters average diameter, and hardness after cold working of 95,6 Rockwell F or better.
- This copper alloy material is manufactured by solution annealing at about 805°C followed by quenching. This method permits producing an alloy material of the above small grain size.
- Copper alloy compositions comprising chrome and/or zirconium are known from GB-A-1 353 430, GB-A-921 795, JP-A-52 3523, JP-A-52 3524 and US-A-3392 016.
- the methods disclosed in JP-A-52 3523 and JP-A-52 3524 don't mention the grain size but don't employ a solid solution treatment, whereas the methods known from GB-A-1353430, GB-A-921 795 and US-A-3392 016 do not teach a grain size control and the non-use of a solution treatment.
- GB-A-1 194 888 discloses a high conductivity copper base alloy consisting of 0.1 to 2.5% chromium, 0.01 to 0.5% phosphorus, 0.001 to 0.25% boron, and the balance copper, apart from conventional impurities.
- This alloy is subjected to a treatment which involves heating for at least 30 minutes at 700 to 975°C, rolling in the aforesaid temperature range, cooling to below 300°C at a rate greater than 550°C per hour, and heating at a temperature of 350 to 550°C for at least one hour. It is to be observed that this document discloses all three of the usual process steps involved in precipitation hardening, i.e. holding for a prolonged period at elevated temperature so as to bring the alloying elements into solid solution, rapid cooling to retain them in solid solution, and finally holding for a significant period at a lower elevated temperature to effect precipitation hardening.
- an electrically conductive precipitation hardenable copper alloy wire material consisting of at least one alloying metal selected from chrome and zirconium, the balance copper, and optionally minor amounts of silicon, germanium, boron and magnesium which comprises the steps of making an ingot, hot-working so as to form the material into a suitable shape, and thereafter repeatedly cold-working and annealing, wherein the steps are performed without subjecting the material to solution treatment so as to obtain said copper alloy material having a grain size number of not less than 7 as defined by JISG 0551, a minimum electrical conductivity of about 88 (IACS %), and a minimum offset yield stress (0.2%) of about 22 kg/mm 2 .
- the most important point of the present invention is the manufacturing of a precipitation hardenable copper alloy material having high electrical conducitivity and mechanical strength by obtaining a grain size number of not less than 7, preferably 8-9 as defined by JIS G 0551 by repeatedly annealing and cold-working the copper alloy material without the solution treatment which has heretofore required a precipitation hardening treatment,
- the suitability for mass production obtained by eliminating the step of the solution treatment is also industrially advantageous.
- the crystal grain size as defined by JIS G 0551 is calculated as follows.
- Making an ingot can be performed by general vacuum melting or atmospheric melting using a carbon melting pot.
- the base metal material preferably comprises a material containing little oxygen, such as a return material or oxygen free copper.
- Quenching in this case means fast cooling from a temperature of 1,200-1,250°C at which the additives are added to a casting temperature of 1,100-1,150°C within a period of only 1-2 minutes.
- This method which adopts a carbon melting pot, is especially advantageous for a chrome-copper alloy, a zirconium-copper alloy, a chrome-zirconium-copper alloy and so on.
- Chrome is preferably added in the form of a base alloy of chrome-copper alloy. This is because the addition of metallic chrome tends to cause segregation due to a difference in melting points and small solid solubility.
- Zirconium may be added only for deoxidation or for inclusion in the alloy.
- Zirconium to be included in the alloy is added separately from zirconium for deoxidation. That is, after sufficiently deoxidizing with zirconium, more zirconium to be included in the alloy may be added.
- the addition of Zr is in general preferably performed at a temperature higher than the melting point of the copper alloy.
- zirconium is added for deoxidation and more zirconium to be included in the alloy is added. This is because Zr is easily oxidized, and the addition of Zr is thus difficult before sufficiently deoxidizing the electrolytic copper.
- Special components such as silicon, germanium, magnesium, boron are added after the deoxidation by zirconium as needed. This is because addition of these elements after sufficient deoxidation results in a better yield. Boron is added simultaneously with chrome as a base metal.
- the ingot making method of the Cr-Zr-Cu alloy may be summarized as follows:
- the features of the copper alloy melted by this method are found to be the same as those of a copper alloy obtained by a conventional vacuum melting method, and have the following advantages.
- the atmospheric melting method which uses a carbon melting pot is advantageous in that it does not require special equipment as in the vacuum melting method and the manufacturing cost may be made less.
- This atmospheric melting method may be advantageously applicable particularly to alloys such as 0.05-1.5% Cr-Cu, preferably 0.3-1.5% Cr-Cu, more preferably 0.3-0.9% Cr-Cu; 0.05-0.5% Zr-Cu, preferably 0.1-0.5% Zr-Cu, more preferably 0.1-0.4% Zr-Cu; 0.3-1 % Cr, 0.1-0.5% Zr, and the balance of Cu; and Cu alloys containing further 0.005-0.1%, preferably 0.01-0.03% (all by weight) of silicon, germanium, boron or magnesium in addition to above ranges of Cr and Zr.
- alloys such as 0.05-1.5% Cr-Cu, preferably 0.3-1.5% Cr-Cu, more preferably 0.3-0.9% Cr-Cu; 0.05-0.5% Zr-Cu, preferably 0.1-0.5% Zr-Cu, more preferably 0.1-0.4% Zr-Cu; 0.3-1 % Cr, 0.1-0.5% Zr, and the balance of Cu; and Cu alloys containing further 0.005-0.1%, preferably 0.01
- the copper alloy material is repeatedly annealed and cold-worked after hot-working in order to obtain optimum results.
- the alloy of the above composition was hot-worked at a temperature of 700-850°C by the atmospheric melting method using a carbon melting pot so as to obtain a wire of 7-10 mm in diameter. Then thus obtained wire was cold-worked after acid cleaning into a wire of 2 mm in diameter. After annealing it at a temperature of 500-650°C, it was further cold-worked into a wire of 0.26 mm in diameter.
- Table II The characteristics of a copper alloy of cold working finish, a copper alloy of annealing finish at a temperature of 550°C, a copper alloy obtained by a conventional precipitation hardening treatment and pure copper are shown in Table II.
- the evaluation method was as follows:
- the specific resistance was measured at room temperature and was converted, taking 0.7241 (International Standard copper specific resistance) as 100.
- a tensile force required to break (kg/mm 2 ).
- Presence or absence of flexibility when twisted in wire form Presence or absence of flexibility when twisted in wire form.
- the grain forms are, in an alloy of rolling finish, relatively elongated and, in an alloy of annealing finish, relatively circular.
- alloys with a grain size number of not less than 7 manufactured by repeated anneal- ings and cold workings without requiring the solution treatment in accordance with the method of the present invention are shown in Table III. These alloys are an alloy (A) of 1% by weight of chrome and copper; an alloy (B) of 0.15% by weight of zirconium and copper an alloy (C) of 0.7% by weight of chrome, 0.3% by weight of zirconium and copper; an alloy (D) of 1 % by weight of chrome, 0.03% by weight of silicon and copper; an alloy (E) of 0.15% by weight of zirconium, 0.03% by weight of silicon and copper; and an alloy (F) of 0.7% by weight of chrome, 0.15% by weight of zirconium, 0.03% by weight of silicon and copper.
- Silicon, germanium, boron, magnesium and so on are effective for improving the mechanical strength and for suppressing the generation of coarse grains.
- the electrically conductive copper alloy manufactured by the method of the present invention may be applied in wide range including cables forwelders, elevator cables, jumpers for vehicles, crane cables, trolly hard copper twisted wires of cable rack wires for power stations and substations. lead wires and so on.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Conductive Materials (AREA)
Claims (1)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9606779A JPS5620136A (en) | 1979-07-30 | 1979-07-30 | Copper alloy member |
| JP96067/79 | 1979-07-30 | ||
| JP99884/79 | 1979-08-07 | ||
| JP9988479A JPS5625940A (en) | 1979-08-07 | 1979-08-07 | Refinig method of copper alloy |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0023362A1 EP0023362A1 (de) | 1981-02-04 |
| EP0023362B1 EP0023362B1 (de) | 1985-06-19 |
| EP0023362B2 true EP0023362B2 (de) | 1993-04-28 |
Family
ID=26437313
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19800104479 Expired - Lifetime EP0023362B2 (de) | 1979-07-30 | 1980-07-29 | Verfahren zur Herstellung einer elektrisch leitfähigen Kupferlegierung |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0023362B2 (de) |
| DE (1) | DE3070776D1 (de) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4352134A (en) * | 1979-11-19 | 1982-09-28 | International Business Machines Corporation | Magnetic head assembly with corrosion resistant conductive wire |
| JPS59117144A (ja) * | 1982-12-23 | 1984-07-06 | Toshiba Corp | リ−ドフレ−ムおよびその製造方法 |
| US4749548A (en) * | 1985-09-13 | 1988-06-07 | Mitsubishi Kinzoku Kabushiki Kaisha | Copper alloy lead material for use in semiconductor device |
| EP0299605B1 (de) * | 1987-05-26 | 1995-11-15 | Nippon Steel Corporation | Eisen-Kupfer-Chrom-Legierung für einen hochfesten Leiterrahmen oder ein Steckstiftgitter und Verfahren zu ihrer Herstellung |
| EP0569036B1 (de) * | 1992-05-08 | 1998-03-11 | Mitsubishi Materials Corporation | Draht für elektrische Bahnstrecke und Verfahren zur Herstellung desselben |
| US5705125A (en) * | 1992-05-08 | 1998-01-06 | Mitsubishi Materials Corporation | Wire for electric railways |
| US5306465A (en) * | 1992-11-04 | 1994-04-26 | Olin Corporation | Copper alloy having high strength and high electrical conductivity |
| US5486244A (en) * | 1992-11-04 | 1996-01-23 | Olin Corporation | Process for improving the bend formability of copper alloys |
| US5370840A (en) * | 1992-11-04 | 1994-12-06 | Olin Corporation | Copper alloy having high strength and high electrical conductivity |
| DE19530673A1 (de) * | 1994-09-15 | 1996-03-21 | Siemens Ag | Oberleitungsdraht einer elektrischen Hochgeschwindigkeitsbahnstrecke und Verfahren zu dessen Herstellung |
| CN105686897B (zh) * | 2014-11-28 | 2019-03-19 | 先健科技(深圳)有限公司 | 管腔支架与其预制件、管腔支架与其预制件的制备方法 |
| CN111621666B (zh) * | 2020-06-22 | 2021-05-07 | 陕西斯瑞新材料股份有限公司 | 一种Cu-Cr系列合金板带的轧制方法 |
| CN112301251A (zh) * | 2020-09-25 | 2021-02-02 | 中铜华中铜业有限公司 | 一种时效强化型Cu-Cr-Zr合金板/带材及其制备方法 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB508330A (en) * | 1937-04-02 | 1939-06-29 | Philips Nv | Improvements in or relating to wire-shaped bodies of high tensile strength and smallspecific resistance |
| GB921795A (en) * | 1961-01-27 | 1963-03-27 | Mallory Metallurg Prod Ltd | Improvements in and relating to copper-base alloys |
| NL295109A (de) * | 1962-12-26 | |||
| GB1094579A (en) * | 1965-10-15 | 1967-12-13 | American Metal Climax Inc | Copper-zirconium-magnesium alloy |
| SU515818A1 (ru) * | 1971-07-20 | 1976-05-30 | Государственный Научно-Исследовательский И Проектный Институт Сплавов И Обработки Цветных Металлов | Сплав на основе меди |
-
1980
- 1980-07-29 DE DE8080104479T patent/DE3070776D1/de not_active Expired
- 1980-07-29 EP EP19800104479 patent/EP0023362B2/de not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0023362B1 (de) | 1985-06-19 |
| DE3070776D1 (en) | 1985-07-25 |
| EP0023362A1 (de) | 1981-02-04 |
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| APAH | Appeal reference modified |
Free format text: ORIGINAL CODE: EPIDOSCREFNO |