CN1254554C - High-strength and high-conductivity RE-Cu alloy and its production process - Google Patents
High-strength and high-conductivity RE-Cu alloy and its production process Download PDFInfo
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- CN1254554C CN1254554C CN 02148648 CN02148648A CN1254554C CN 1254554 C CN1254554 C CN 1254554C CN 02148648 CN02148648 CN 02148648 CN 02148648 A CN02148648 A CN 02148648A CN 1254554 C CN1254554 C CN 1254554C
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 117
- 239000000956 alloy Substances 0.000 claims abstract description 117
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000005098 hot rolling Methods 0.000 claims abstract description 13
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 10
- 238000005097 cold rolling Methods 0.000 claims abstract description 9
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims description 35
- 230000008018 melting Effects 0.000 claims description 31
- 239000010949 copper Substances 0.000 claims description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 22
- 229910052802 copper Inorganic materials 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 14
- 229910052726 zirconium Inorganic materials 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 239000011651 chromium Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010791 quenching Methods 0.000 claims description 8
- 238000005275 alloying Methods 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 claims description 6
- FQVNUZAZHHOJOH-UHFFFAOYSA-N copper lanthanum Chemical compound [Cu].[La] FQVNUZAZHHOJOH-UHFFFAOYSA-N 0.000 claims description 6
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- XTYUEDCPRIMJNG-UHFFFAOYSA-N copper zirconium Chemical compound [Cu].[Zr] XTYUEDCPRIMJNG-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000004100 electronic packaging Methods 0.000 abstract 1
- 239000005022 packaging material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002184 metal Substances 0.000 description 5
- 229910000967 As alloy Inorganic materials 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 229910017526 Cu-Cr-Zr Inorganic materials 0.000 description 3
- 229910017810 Cu—Cr—Zr Inorganic materials 0.000 description 3
- 239000003507 refrigerant Substances 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- 229910000691 Re alloy Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 229910019580 Cr Zr Inorganic materials 0.000 description 1
- 229910017824 Cu—Fe—P Inorganic materials 0.000 description 1
- 229910017876 Cu—Ni—Si Inorganic materials 0.000 description 1
- 229910017061 Fe Co Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
The present invention discloses a high-strength and high-conductivity rare earth (RE)-Cu alloy and a production method thereof and relates to a high-strength and high-conductivity copper alloy for lead frames, electrode alloys and electronic packaging materials and a manufacturing technology thereof. In the present invention, microalloy elements, such as La, Zn, Fe (or Co) and Ti are added to a traditional CuCrZr alloy which is used as a basis, and the combination property of the alloy can achieve balance through the processes such as hot rolling, solution treatment, cold rolling, ageing, etc. Compared with the traditional CuCrZr alloy, the electric conductivity, the tensile strength and the hardness of the alloy are obviously improved; the present invention has the advantages of simple preparation method, low raw material cost and extensive application to the lead frames, the electrode alloys, connectors, etc. in an electronic industry.
Description
Technical field
The present invention relates to a Copper base alloy and manufacturing technology thereof, relate in particular to a kind of high-strength high conductivities such as lead frame, electrode metal and junctor copper alloy and manufacture method thereof of being used for.
Background technology
Because have favorable conductive heat conductivility, corrosion resistance nature, intensity, fatigue property and be easy to characteristics such as manufacturings, copper and alloy thereof have obtained application widely in electronics, electric power, machinery and field of aerospace, become the important electron metallic substance.Therein, Cu-Cr-Zr is that alloy is the high-strength high conductivity alloy of a class widespread use, and principal feature is to have high specific conductivity.But its intensity is on the low side.For further satisfying the various performance requriementss of electronic units such as lead frame,, need further improve the performance of alloy as performances such as intensity, specific conductivity, welding, etchings.
At present countries in the world are just at the active development high-intensity high-conductivity copper alloy, as C18040 (Cu-0.3Cr-0.25Sn-0.5Zn) and (Cu-0.3Cr-0.1Zr-0.05Mg-0.02Si) etc.Japan greatly develops lead frame copper alloy from the seventies in last century, its typical case's representative is companies such as Mitsubishi, Sumitomo, Kobe, mining industry metal, Furukawa.Also applied for many patents around each company of these alloy products, as: US1658186,1778668,2185958,2137282,3027508,4466939, JP213847/83 or the like.These patents are with regard to alloy ingredients such as Cu-Fe-P system, Cu-Ni-Si system and Cu-Cr-Zr systems, preparation method and the improvement of a certain property carried out discussing and the proposition intellectual property protection.
What U.S. Olin Corp 1993 application and the granted patent CN1101081 that obtained in 1998 related to is alloy, disclose a kind ofly to contain chromium, zirconium, cobalt and/or iron, and the copper base alloy of special additive such as titanium and the method for producing this copper alloy; A kind of processing method is produced the copper alloy with high strength and high conductivity; Another kind of processing method is produced has more high strength but electric conductivity has the copper alloy of a small amount of reduction; What Japan Nippon Mining and Metals Co., Ltd plucked that mandate CN1115789 that China obtains relates in 1999 also is that Cu-Cr-Zr is an alloy.But the complex manufacturing of above-mentioned patent, alloying element do not contain rare earth element yet, and plant produced is difficulty relatively.
The domestic unit of China has also applied for the patent that some are relevant with the high-strength high conductivity alloy.What patent CN1250816 discussed is the Cu-Cr-Zr-B-Nb-RE alloy, and its composition is comparatively complicated, is mainly used in the resistance welding electrode material.What patent CN1285417 also related to is a kind of high-conductivity copper base alloy for electrode of resistance welding, and its composition is a zirconium Cu-Zr-B-Nb-Mg-RE alloy, and its specific conductivity is 48MS/m, and hardness (HRB) is 65, and performance is not high.Patent CN1270434A, the alloy that relates to mainly are Cu-Zr-Zn-Re high-strength highly-conductive alloys, but its Zn content is higher, mainly are to be applied to bullet train asynchronous traction motor sliver and end ring.Patent CN1231343 relates to a kind of Cu-Cr-Y copper base alloy electrode material and preparation method thereof, belongs to the alloy conductive material, and it mainly is to adopt the powder metallurgy method manufactured materials, and cost is higher.
In sum, above-mentioned domestic and international patent does not all relate to or detailed description this patent proposes high-strength high conductivity rare-earth copper alloy and manufacture method thereof.
Summary of the invention
The objective of the invention is to propose a kind of copper alloy and manufacture method thereof with high-strength high conductivity, on the basis of traditional CuCrZr alloy, add trace alloying element La, Zn and Fe (or Co) and Ti, and by technologies such as hot rolling, solution treatment, cold rolling, timeliness, make the over-all properties of its alloy reach balance, and cost is reduced, thereby realize the widespread use of its lead frame, electrode metal and junctor etc. in electron trade.
The high-strength high conductivity rare-earth copper alloy that the present invention proposes, containing weight percent is 0.01-0.30% rare-earth elements of lanthanum and/or cerium, 0.05-1.0% zinc, 0.01-1.0% chromium, the 0.01-0.6% zirconium, 0.1-1.0% iron or cobalt and 0.05-0.8% titanium, all the other are copper.
The present invention also provides a kind of method of making above-mentioned rare-earth copper alloy, and this method comprises the steps:
(1) melting: adopt electrolytic copper, copper-10% chromium master alloy, copper-10% zirconium master alloy, copper-5% lanthanum master alloy, copper-30% zinc master alloy, add as bed material with pure iron and pure titanium or with pure cobalt and pure titanium, its addition sequence: at first add electrolytic copper, copper-chromium master alloy, melting 20～30 minutes, add copper-lanthanum master alloy then, melting 1～3 minute adds copper-zinc master alloy and copper-zirconium master alloy at last, and melting was cast after 1～3 minute;
(2) hot rolling: 850～950 ℃ of insulations 1～4 hour, it was rolling to carry out 50～80% distortion then on the hot rolls of routine with above-mentioned cast alloys;
(3) solution treatment: the sheet material after rolling is packed in the heat treatment furnace,, its alloying element is fully dissolved in the copper matrix, carry out quench treatment then 950～1050 ℃ of insulations 10～30 minutes down;
(4) cold rolling: the alloy after will quenching carries out 60～90% deformation process;
(5) ageing treatment: alloy is incubated 1～24 hour at 400～600 ℃;
(6) finish to gauge: alloy carried out 30～50% deformation process.
The present invention has added trace alloying element La, Zn and Fe (or Co) and Ti on the basis of CuCrZr alloy, and by technologies such as hot rolling, solution treatment, cold rolling, timeliness, make the over-all properties of its alloy reach balance, its specific conductivity, tensile strength and hardness and traditional copper base alloy phase ratio are significantly improved.Its preparation method is simple, and raw materials cost is low, thereby can realize the widespread use of its lead frame in electron trade, electrode metal and junctor etc.
Description of drawings
Fig. 1 is a main technique schema of the present invention.
Embodiment
The centre is cutd open alloy and can be bought on market, also can adopt pure metal to be smelted into master alloy and obtain.
Embodiment 1:
The CuCrZrZnLa alloy adopts following raw material melting: electrolytic copper, copper-10% chromium master alloy, copper-10% zirconium master alloy, copper-5% lanthanum master alloy, copper-30% zinc master alloy.The composition of alloy sees Table 1 embodiment 1.
1. melting: the melting equipment that adopts industry to use carries out melting.The order that alloy adds is at first adding electrolytic copper, copper-chromium master alloy, and fusing back melting 20 minutes, adding copper-lanthanum master alloy melting 3 minutes added copper-zinc master alloy, copper-melting of zirconium master alloy 3 minutes at last, cast then.
2. hot rolling: ingot casting is heated to 900 ℃ after peeling, is incubated 2 hours, carries out 70% deformation process.
3. solution treatment: will be heated to 970 ℃ through the alloy of deformation process, and be incubated 30 minutes, in the entry of quenching;
4. cold rolling: as alloy to be carried out 85% deformation process;
5. ageing treatment: alloy at 460 ℃, is incubated 2 hours;
6. finish to gauge: alloy is carried out 40% deformation process, promptly make the CuCrZrZnLa alloy.
After hot and cold processing treatment such as above melting, hot rolling, solid solution, cold deformation and timeliness, reach following performance: specific conductivity 80%IACS, tensile strength 553.6MPa, hardness Hv170.
Embodiment 2:
The CuCrZrZnLaFeTi alloy adopts following raw material melting: electrolytic copper, copper-10% chromium master alloy, copper-10% zirconium master alloy, copper-5% lanthanum master alloy, copper-30% zinc master alloy, pure iron, pure titanium.The composition of alloy sees Table 1 embodiment 2.
1. melting: the melting equipment that adopts industry to use carries out melting.The order that alloy adds is at first adding electrolytic copper, copper-chromium master alloy, pure iron, pure titanium, fusing back melting 30 minutes, added copper-lanthanum master alloy melting 3 minutes, added copper-zinc master alloy, copper-melting of zirconium master alloy at last 2 minutes, cast then;
2. hot rolling: ingot casting is heated to 880 ℃ after peeling, is incubated 3 hours, carries out 70% deformation process;
3. solution treatment: alloy is heated to 1000 ℃ of insulations 20 minutes, in the quick refrigerant such as the entry of quenching;
4. cold rolling: as alloy to be carried out 90% deformation process;
5. ageing treatment: with alloy 500 ℃ of insulations 4 hours down;
6. finish to gauge: alloy carried out 50% deformation process and promptly make the CuCrZrZnLaFeTi alloy.
After hot and cold processing treatment such as hot rolling, solid solution, cold deformation and timeliness, reach following performance: specific conductivity 65%IACS, tensile strength 641.4MPa, hardness Hv195.
Embodiment 3:
CuCrZrZnCeCoTi adopts following molten alloy: electrolytic copper, copper-10% chromium master alloy, copper-10% zirconium master alloy, copper-5% cerium master alloy, copper-30% zinc master alloy, pure cobalt, pure titanium.The composition of alloy sees Table 1 embodiment 3.
1. melting: the melting equipment that adopts industry to use carries out melting.The order that alloy adds is at first adding electrolytic copper, copper-chromium master alloy, pure cobalt, pure titanium, fusing back melting 30 minutes, added copper-lanthanum master alloy melting 3 minutes, added copper-zinc master alloy, copper-melting of zirconium master alloy at last 1 minute, cast then;
2. hot rolling: ingot casting is heated to 880 ℃ after peeling, is incubated 2 hours, carries out 70% distortion;
3. solution treatment: alloy is heated to 960 ℃ of insulations 30 minutes, in the quick refrigerant such as the entry of quenching;
4. cold rolling: as alloy to be carried out 90% deformation process;
5. ageing treatment: with alloy 450 ℃ of insulations 12 hours;
6. finish to gauge: alloy carried out 50% deformation process;
After hot and cold processing treatment such as hot rolling, solid solution, cold deformation and timeliness, reach following performance: specific conductivity 69%IACS, tensile strength 616.2MPa, hardness Hv186.
Embodiment 4:
CuCrZrZnLaCoTi adopts following raw material molten alloy: electrolytic copper, copper-10% chromium master alloy, copper-10% zirconium master alloy, copper-5% lanthanum master alloy, copper-30% zinc master alloy, pure cobalt, pure titanium.The composition of alloy sees Table 1 embodiment 4.
1. melting: the melting equipment that adopts industry to use carries out melting.The order that alloy adds is at first adding electrolytic copper, copper-chromium master alloy, pure cobalt, pure titanium, fusing back melting 30 minutes, added copper-lanthanum master alloy melting 1 minute, added copper-zinc master alloy, copper-melting of zirconium master alloy at last 1 minute, cast then:
2. hot rolling: ingot casting is heated to 880 ℃ after peeling, is incubated 2 hours, carries out 70% distortion;
3. solution treatment: alloy is heated to 990 ℃ of insulations 30 minutes, in the quick refrigerant such as the entry of quenching;
4. cold rolling: as alloy to be carried out 80% deformation process;
5. ageing treatment: with alloy 450 ℃ of insulations 8 hours;
6. finish to gauge: alloy carried out 50% deformation process; After hot and cold processing treatment such as hot rolling, solid solution, cold deformation and timeliness, reach following performance: specific conductivity 70%LACS, tensile strength 608.2MPa, hardness Hv179.
The chemical ingredients of table 1. alloy:
| Alloying constituent | Cr | Zr | Zn | Fe | Co | Ti | Rare earth | Cu | |
| Comparative alloy | CuCrZrZn | 0.38 | 0.25 | 0.21 | Surplus | ||||
| Embodiment 1 | CuCrZrZnLa | 0.35 | 0.14 | 0.24 | 0.05 | Surplus | |||
| Embodiment 2 | CuCrZrZnLaFeTi | 0.37 | 0.15 | 0.23 | 0.47 | 0.25 | 0.10 | Surplus | |
| Embodiment 3 | CuCrZrZnCoTiCe | 0.37 | 0.16 | 0.20 | 0.46 | 0.23 | 0.04 | Surplus | |
| Embodiment 4 | CuCrZrZnCoTiLa | 0.21 | 0.11 | 0.20 | 0.35 | 0.19 | 0.01 | Surplus |
The salient features of above alloy and C19400 alloy sees Table 2:
The contrast of table 2. alloy salient features:
| Alloying constituent | Tensile strength (MPa) | Unit elongation (%) | Specific conductivity (%IACS) |
| Comparative alloy | 510.2 | ≥5 | 77 |
| C19400 | 362～568 | 4～5 | 55～65 |
| Embodiment 1 | 553.6 | ≥5 | 80 |
| Embodiment 2 | 641.4 | ≥5 | 65 |
| Embodiment 3 | 616.2 | ≥5 | 69 |
| Embodiment 4 | 608.2 | ≥5 | 70 |
Claims (2)
1. high-strength high conductivity rare-earth copper alloy, it is characterized in that: it is 0.01-0.30% rare-earth elements of lanthanum and/or cerium that this alloy contains weight percent, 0.05-1.0% zinc, 0.01-1.0% chromium, 0.01-0.6% zirconium, 0.1-1.0% iron or cobalt, the 0.05-0.8% titanium, all the other are copper.
2. implement the manufacture method of rare-earth copper alloy according to claim 1, it is characterized in that this method comprises the steps:
(1) melting: adopt electrolytic copper, copper-10% chromium master alloy, copper-10% zirconium master alloy, copper-5% lanthanum master alloy, copper-30% zinc master alloy, add as bed material with pure iron and pure titanium or with pure cobalt and pure titanium, its addition sequence: at first add electrolytic copper, copper-chromium master alloy, melting 20～30 minutes, add copper-lanthanum master alloy then, melting 1～3 minute adds copper-zinc master alloy and copper-zirconium master alloy at last, and melting was cast after 1～3 minute;
(2) hot rolling: 850～950 ℃ of insulations 1～4 hour, it was rolling to carry out 50～80% distortion then on the hot rolls of routine with cast alloys;
(3) solution treatment: the sheet material after rolling is packed in the heat treatment furnace,, its alloying element is fully dissolved in the copper matrix, carry out quench treatment then 950～1050 ℃ of insulations 10～30 minutes down;
(4) cold rolling: the alloy after will quenching carries out 60～90% deformation process;
(5) ageing treatment: alloy is incubated 1～24 hour at 400～600 ℃;
(6) finish to gauge: alloy carried out 30～50% deformation process.
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| CN 02148648 CN1254554C (en) | 2002-11-15 | 2002-11-15 | High-strength and high-conductivity RE-Cu alloy and its production process |
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| CN100469923C (en) * | 2006-09-27 | 2009-03-18 | 苏州有色金属加工研究院 | High temperature copper alloy for lead frame and its making process |
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