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, all the other are copper.
For further improving intensity, also can add weight percent on the basis of said components is 0.1-1.0% iron or cobalt element and 0.05-0.8% titanium elements.
The present invention also provides a kind of method of making above-mentioned alloy, and this method comprises the steps:
(1) melting: adopting electrolytic copper, copper-10% chromium master alloy, copper-10% zirconium master alloy, copper-5% lanthanum master alloy, copper-30% zinc master alloy is raw material, its addition sequence is at first adding electrolytic copper, copper-chromium master alloy, melting 20~30 minutes, add copper-lanthanum master alloy then, melting 1~3 minute, add copper-zinc master alloy and copper-zirconium master alloy at last, 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.
In above-mentioned fusion process,, should add as bed material if add pure iron, pure cobalt, pure titanium.
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.
Embodiment
Master alloy 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%IACS, 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 |