CN1861819A - Non-vacuum smelting casting tech. of Cu-Cr-Zr alloy and Cu-Zr alloy - Google Patents
Non-vacuum smelting casting tech. of Cu-Cr-Zr alloy and Cu-Zr alloy Download PDFInfo
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- CN1861819A CN1861819A CN 200610046446 CN200610046446A CN1861819A CN 1861819 A CN1861819 A CN 1861819A CN 200610046446 CN200610046446 CN 200610046446 CN 200610046446 A CN200610046446 A CN 200610046446A CN 1861819 A CN1861819 A CN 1861819A
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Abstract
This invention relates to an anti-vacuum method to cast alloy Cu-Cr-Zr and Cu-Zr. The processes of producing alloy Cu-Cr-Zr is as follows: a. making the element Cr, Zr, Al and Mg which are apt to oxygenizing into intermediate alloys, b. d and heated to 1350 deg.C, sampling after adding into the intermediate alloys Cu-Cr and melting the mixture, then analyzing the Cr content of sample. If the content of Cr is accepted, adding into the intermediate alloys Cu-Al, then adding into intermediate alloys Cu-Zr-Mg after heating. When the temperature is high enough to cast, we can cast to get alloy Cu-Cr-Zr. The processes of producing alloy Cu-Zr is as follows: a. making the element Zr, Al and Mg which are apt to oxygenizing into intermediate alloy, it can be used as the material subsequently, b. after melting the copper and covering reagent together, adding into the alloy Cu-Al and heating, then adding into the intermediate alloy Cu-Zr-Mg, when it reaches the casting temperature, the crystallizer and launder are covered by the carbon ink, we finish the casting and get the alloy Cu-Zr. This method gets rid of the production of alloys Cu-Cr-Zr and Cu-Zr with vacuum furnace and the high cost of the alloy.
Description
One, technical field: the antivacuum founding that the present invention relates to a kind of copper alloy to high strength, high conductivity, particularly to Cu-Cr-Zr alloy and Cu-Zr alloy under atmospheric condition, realize the production technique of the founding of these two kinds of alloys with the mode of induction furnace melting and direct chill casting.
Two, background technology: Cu-Cr-Zr alloy (C18150) and Cu-Zr alloy (C15000) are the copper alloy trades mark in U.S.'s metallic substance and the test ASTM of the association standard, this alloy has the characteristics of high strength, high conductivity, being mainly used in the electrode of making automatic welding machine, electronic industry frame material, electric railway locomotive slip, large cast steel crystallizer material etc., is the alloy that market outlook are arranged very much.The founding of these two kinds of alloys is first procedures of producing this alloy wire, bar, sheet material.At present; the founding of these two kinds of alloys; domesticly generally adopt vacuum oven production; this mode production efficiency is low, cost is high; and the maximum capacity vacuum oven that domestic quality reaches a standard is 500Kg; can not satisfy electric railway locomotive slip, large cast steel crystallizer piece of material weight greater than 1 ton requirement; and import high-capacity vacuum stove; cost an arm and a leg; adopted non-vacuum melting technique in developed countries such as the U.S., Japan; but all need special melting equipment, increased a lot of gas shield measures, facility investment is big.Because the limitation of casting technology has seriously restricted expansion, popularization and the application of these two kinds of alloy production scales.
Three, summary of the invention:
1, goal of the invention: the antivacuum founding that the invention provides a kind of Cu-Cr-Zr alloy and Cu-Zr alloy, promptly under atmospheric condition, adopt power frequency or medium-frequency induction furnace melting, the direct chill casting mode is produced Cu-Cr-Zr alloy (C18150) and Cu-Zr alloy (C15000), be used for substituting the vacuum casting production technique that generally adopts at present both at home and abroad, solve the present situation that production cost is too high, production efficiency is lower, product specification is subjected to the vacuum oven capacity limit, enlarge the range of application and the field of these two kinds of alloy materials.
2, technical scheme: the present invention is achieved through the following technical solutions:
A kind of antivacuum founding of Cu-Cr-Zr alloy is characterized in that: it is undertaken by following step:
A. get Cr, Zr, the easy oxidation element of Al, Mg, they are made master alloy CuCr
6, CuZr
10Mg
0.3, CuAl
10, as the raw material of follow-up adding;
B. prepare the Cu-Cr-Zr alloy: copper and insulating covering agent are warming up to 1350～1400 ℃ after the fusing together in induction furnace, add CuCr
6Master alloy is treated its fusing back sampling, is analyzed the Cr composition, and Cr is qualified, and the back adds CuAl
10Heating up in the back, makes Al fusing fully in melt, adds CuZr then
10Mg
0.3Master alloy and be warming up to 1350～1400 ℃ after cast, with carbon black crystallizer, chute are covered fully during casting, casting promptly obtains the Cu-Cr-Zr alloy after finishing.
Insulating covering agent is dewatering borax and glass, and dewatering borax and glass weight ratio are 3: 1, and they are covered copper melts after copper melts fully, make copper melts and air insulated.
Casting is finished in 1/3 o'clock melt in stove of whole melt weight and is replenished CuZr by 0.08～0.2% of Zr ingredients by weight ratio among the above-mentioned steps b
10Mg
0.3Master alloy.
The ingredients by weight of Cr ratio is 0.7～1.0% among the above-mentioned steps b, and the ingredients by weight ratio of Al is 0.10～0.25%, and the ingredients by weight ratio of Zr is 0.25～0.45%.
When the diameter of casting was φ 120～260mm ingot casting, casting rate was 0.8mm/s～1.5mm/s among the above-mentioned steps b.
A kind of antivacuum founding of Cu-Zr alloy is characterized in that: it is undertaken by following step:
A. get Zr, Al, the easy oxidation element of Mg, they are made master alloy CuZr
10Mg
0.3, CuAl
10, as the raw material of follow-up adding;
B. prepare the Cu-Zr alloy: copper and insulating covering agent after the fusing, are added CuAl together in induction furnace in fused copper water
10And improve temperature Al is dissolved fully, add CuZr
10Mg
0.3After improving temperature to 1350～1400 ℃, cast, with carbon black crystallizer, chute are covered fully during casting, promptly get the Cu-Zr alloy after casting is finished.
Insulating covering agent is dewatering borax and glass, and dewatering borax and glass weight ratio are 3: 1, and they are covered copper melts after copper melts fully, make copper melts and air insulated.
Among the above-mentioned steps b casting finish whole melt weight 1/3 and replenished CuZr by 0.08～0.2% of Zr ratio of components weight in the melt in stove respectively at 2/3 o'clock
10Mg
0.3Master alloy.
The ingredients by weight of Al ratio is 0.10～0.25% among the above-mentioned steps b, and the ingredients by weight ratio of Zr is 0.30～0.45%.
Last two state among the step b when the casting diameter is the ingot casting of φ 120～260mm, and casting rate is 0.8mm/s～1.5mm/s.
3, advantage and effect: by the enforcement of technical solution of the present invention, can solve the low problem of production cost height, production efficiency that Cu-Cr-Zr alloy and Cu-Zr alloy generally adopt the vacuum oven founding well, and the equipment input of antivacuum founding only is with 1/10 of capacity vacuum oven smelting-casting equipment, production efficiency is 3 times with the capacity vacuum oven, and production cost is with 1/2 of capacity vacuum oven.The present invention not only increases substantially production efficiency, reduces cost, and can satisfy single product weight such as electric railway locomotive slip, cast steel crystallizer well greater than 1 ton requirement, solved the great technical barrier that perplexs the domestic same industry, very important industrial promotional value is arranged, fill up a blank of domestic this alloy production technology, immeasurable realistic meaning is arranged for the technical progress and the capability of independent innovation construction that promote the internal copper processing industry.
In good time, the suitably adding of Al element in the production technique of the present invention, to under atmospheric condition, line frequency furnace or the semicontinuous mode of intermediate frequency furnace melting are cast, and realize the founding production of Cu-Cr-Zr alloy (C18150) and Cu-Zr alloy (C15000), have played very crucial stabilizer function.Evidence, Al content is controlled between (0.1～0.25%) in the alloy, and neither the electric conductivity to alloy constitutes influence, can stablize well again and live in Cr and Zr element, makes it uniform distribution; CuZr
10Mg
0.3The making of master alloy has also been played vital role to the adding of Zr.
Four, description of drawings: accompanying drawing 1 prepares the schema of Cu-Cr-Zr alloy for the present invention;
Accompanying drawing 2 prepares the schema of Cu-Cr-Zr alloy for another embodiment of the present invention;
Accompanying drawing 3 prepares the schema of Cu-Zr alloy for the present invention;
Accompanying drawing 4 prepares the schema of Cu-Zr alloy for another embodiment of the present invention.
Five, embodiment:
The invention provides a kind of under atmospheric condition, be difficult to realize the Cu-Cr-Zr alloy of founding and the antivacuum founding of Cu-Zr alloy, it has solved principal element Cr and the Zr very easily oxidation in air in the alloy at all, be difficult to join in the melt of Cu, especially Zr is extremely active, under atmospheric condition, as not taking measures, these two kinds of alloys of founding almost are impossible.Therefore, to the production of these two kinds of alloys, domesticly generally adopt vacuum oven production.Domestic vacuum oven capacity is little, and production efficiency is low, and the cost height is difficult to adapt to the market requirement that enlarges day by day both at home and abroad.Technology of the present invention very easily oxidation under atmospheric condition at Cr and Zr, the characteristics that are difficult to alloying, by add trace, the finished product performance not have the Cr that influences and the stablizer Al of Zr, cooperation is with relevant reductor Mg and melt insulating covering agent dewatering borax and glass, realize using power frequency or medium-frequency induction furnace melting, the direct chill casting mode is produced the purpose of these two kinds of alloys.
Embodiment 1:
As shown in Figure 1, the antivacuum founding of Cu-Cr-Zr alloy of the present invention, it is undertaken by following step:
A. earlier the element of Cr, Zr, Al, the easy oxidation of Mg is made CuCr
6, CuZr
10Mg
0.3, CuAl
10Master alloy is as the raw material of follow-up adding;
B. select 1.2 tons of the standard cathode copper that conform to quality requirements for use, join in 1.5 tons of line frequency furnaces, add enough dewatering borax and glass simultaneously as insulating covering agent, borax and weight of glass ratio are 3: 1, with the electrolytic copper fusing, insulating covering agent covers has avoided it directly to contact with air on copper melts; The copper water temp of fusing is brought up to about 1350 ℃～1400 ℃, added CuCr
6Master alloy is treated its fusing, the Chemical Composition of sampling analysis Cr, and its ingredients by weight is than 1.0%; After element is qualified, clamp the CuAl that has calculated with special-purpose hawkbill
10Master alloy is inserted into the following 50mm of liquid level rapidly, slowly unclamps pliers, and Al is fully fused in the melt of Cu-Cr, and the ingredients by weight of Al ratio is controlled at 0.25%; Make the melt that adds behind the Al improve temperature once more, when temperature reaches 1350 ℃～1400 ℃ left and right sides, add CuZr rapidly
10Mg
0.3Master alloy, the ingredients by weight ratio of its Zr is controlled at 0.45%; When improving temperature to 1350 ℃～1400 ℃, see that promptly having a power failure began casting when melt liquid level insulating covering agent in the stove sprayed the little flare of blue look outward, chute and mold liquid level cover tight during casting with carbon black; Finish up to whole stove copper water casting, obtain the Cu-Cr-Zr alloy.
Embodiment 2:
As shown in Figure 2, the antivacuum founding of Cu-Cr-Zr alloy of the present invention, it is undertaken by following step:
A. earlier Cr, Zr, Al, Mg are made CuCr
6, CuZr
10Mg
0.3, CuAl
10Master alloy is stand-by;
B. select 1.2 tons of the standard cathode copper that conform to quality requirements for use, join in 1.5 tons of line frequency furnaces, add enough dewatering borax and glass simultaneously as insulating covering agent, borax and weight of glass ratio are 3: 1, electrolytic copper fusing back is added insulating covering agent, avoid directly contacting with air with copper melts;
C. the copper water temp of fusing is brought up to about 1350 ℃～1400 ℃, added CuCr
6Master alloy is treated its fusing, and the Chemical Composition of sampling analysis Cr is by limit control (ingredients by weight is than 0.7%) on the lower side;
After the d.Cr element is qualified, clamp the CuAl that has calculated with special-purpose hawkbill
10Master alloy is inserted into the following 50mm of liquid level rapidly, slowly unclamps pliers, and Al is fully fused in the melt of Cu-Cr, and the ingredients by weight of Al ratio is controlled at 0.2%;
E. make the melt that adds behind the Al improve temperature once more and suitably replenish insulating covering agent borax and glass, it is tight that melt liquid level is covered, and prevents the scaling loss of Cr.When temperature reaches 1350 ℃～1400 ℃ left and right sides, promptly add CuZr rapidly
10Mg
0.3Master alloy, the ingredients by weight ratio of its Zr is controlled at 0.25%;
When f. improving temperature to 1350 ℃～1400 ℃, see that promptly having a power failure began casting when melt liquid level insulating covering agent in the stove sprayed the little flare of blue look outward, chute and mold liquid level cover tight during casting with carbon black;
G. by the time whole stove copper water watered about 1/3 o'clock, the beginning feeding temperature-raising when treating on the temperature, in time replenishes CuZr rapidly
10Mg
0.3Master alloy 10Kg, the scaling loss of replenishing Zr in the whole casting cycle makes the Zr composition that makes at last in the alloy reach the requirement of standard, finishes up to whole stove copper water casting, obtains the Cu-Cr-Zr alloy.
Embodiment 3:
The preparation technology of Cu-Zr alloy of the present invention is as follows, sees shown in Figure 3:
A. earlier the element of Zr, Al, the easy oxidation of Mg is made CuZr
10Mg
0.3, CuAl
10Master alloy is as the raw material of follow-up adding;
B. select 1.2 tons of the standard cathode copper that conform to quality requirements for use, join in 1.5 tons of line frequency furnaces, electrolytic copper is melted, add enough dewatering borax and glass simultaneously as insulating covering agent, borax and weight of glass ratio are 3: 1, and insulating covering agent covers has avoided it directly to contact with air on copper melts; When being warmed up to 1350～1400 ℃, clamp the CuAl that has calculated with special-purpose hawkbill
10Master alloy is inserted into the following 50mm of liquid level rapidly, slowly unclamps pliers, and Al is fully fused in the melt of Cu, and the ingredients by weight of Al ratio is controlled at 0.25%; Promptly add CuZr than 0.45% when being warmed up to 1350～1400 ℃ once more by the Zr ingredients by weight
10Mg
0.3Master alloy continues to send electricity, after the fusing that heats up, begins casting when reaching 1350 ℃, and in casting cycle, chute and crystallizer cover with carbon black, finish up to casting, obtain the Cu-Zr alloy.
Embodiment 4:
The preparation technology of Cu-Zr alloy of the present invention is as follows, as shown in Figure 4, earlier the element of Zr, Al, the easy oxidation of Mg is made CuZr
10Mg
0.3, CuAl
10Master alloy is as the raw material of follow-up adding; After 1.2 tons electrolytic copper fusing, add enough dewatering borax and glass and cover, when being warmed up to 1350～1400 ℃, clamp the CuAl that has calculated with special-purpose hawkbill
10Master alloy is inserted into the following 50mm of liquid level rapidly, slowly unclamps pliers, and Al is fully fused in the melt of Cu, and the ingredients by weight of Al ratio is controlled at 0.15%; Promptly add CuZr than 0.3% when being warmed up to 1350～1400 ℃ once more by the Zr ingredients by weight
10Mg
0.3Master alloy continues to send electricity, after the fusing that heats up, begins casting when reaching 1350 ℃, and in casting cycle, chute and crystallizer cover with carbon black, treats in the stove that copper water has watered 1/3 and 2/3 o'clock feeding temperature-raising, the CuZr of additional 10Kg respectively
10Mg
0.3Master alloy, the scaling loss of replenishing Zr in the whole casting cycle makes the Zr composition that makes at last in the alloy reach the requirement of standard, finishes up to casting, obtains the Cu-Zr alloy.
Claims (10)
1, a kind of antivacuum founding of Cu-Cr-Zr alloy, it is characterized in that: it is undertaken by following step:
A. get Cr, Zr, the easy oxidation element of Al, Mg, they are made master alloy CuCr
6, CuZr
10Mg
0.3, CuAl
10, as the raw material of follow-up adding;
B. prepare the Cu-Cr-Zr alloy: copper and insulating covering agent after the fusing, are warming up to 1350 ℃～1400 ℃ together in induction furnace, add CuCr
6Master alloy is treated its fusing back sampling, is analyzed the Cr composition, and Cr is qualified, and the back adds CuAl
10Heating up and make Al fusing fully in melt in the back, adds CuZr then
10Mg
0.3Master alloy and be warming up to 1350～1400 ℃ after cast, with carbon black crystallizer, chute are covered fully during casting, casting promptly obtains the Cu-Cr-Zr alloy after finishing.
2, the antivacuum founding of Cu-Cr-Zr alloy according to claim 1, it is characterized in that: insulating covering agent is dewatering borax and glass, dewatering borax and glass weight ratio are 3: 1, and they are covered melt after copper melts fully, make it and air insulated.
3, the antivacuum founding of Cu-Cr-Zr alloy according to claim 1 is characterized in that: among the above-mentioned steps b when casting finish whole melt weight 1/3 the time, press 0.08～0.2% additional CuZr of Zr ingredients by weight ratio in the melt in stove
10Mg
0.3Master alloy.
4, the antivacuum founding of Cu-Cr-Zr alloy according to claim 1, it is characterized in that: the ingredients by weight of Cr ratio is 0.7～1.0% among the above-mentioned steps b, the ingredients by weight ratio of Al is 0.10～0.25%, and the ingredients by weight ratio of Zr is 0.25～0.45%.
5, the antivacuum founding of Cu-Cr-Zr alloy according to claim 1 is characterized in that: when the casting diameter was the ingot casting of φ 120～260mm, casting rate was 0.8mm/s～1.5mm/s among the above-mentioned steps b.
6, a kind of antivacuum founding of Cu-Zr alloy, it is characterized in that: it is undertaken by following step:
A. get Zr, Al, the easy oxidation element of Mg, they are made master alloy CuZr
10Mg
0.3, CuAl
10, as the raw material of follow-up adding;
B. prepare the Cu-Zr alloy: copper and insulating covering agent after the fusing, are added CuAl together in induction furnace in fused copper water
10And heat up Al is melted fully, add CuZr
10Mg
0.3Cast after being warming up to 1350～1400 ℃, with carbon black crystallizer, chute are covered fully during casting, promptly obtain the Cu-Zr alloy after casting is finished.
7, the antivacuum founding of Cu-Zr alloy according to claim 6, it is characterized in that: insulating covering agent is dewatering borax and glass, dewatering borax and glass weight ratio are 3: 1, and they are covered copper melts after copper melts fully, make copper melts and air insulated.
8, the antivacuum founding of Cu-Zr alloy according to claim 6 is characterized in that: among the above-mentioned steps b casting finish whole melt weight 1/3 and replenished CuZr by 0.08～0.2% of Zr ratio of components weight in the melt in stove respectively at 2/3 o'clock
10Mg
0.3Master alloy.
9, the antivacuum founding of Cu-Zr alloy according to claim 6 is characterized in that: the ingredients by weight of Al ratio is 0.10～0.25% among the above-mentioned steps b, and the ingredients by weight ratio of Zr is 0.30～0.45%.
10, the antivacuum founding of Cu-Zr alloy according to claim 6 is characterized in that: when the casting diameter was the ingot casting of φ 120～260mm, casting rate was 0.8mm/s～1.5mm/s among the above-mentioned steps b.
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Cited By (7)
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| CN101906547A (en) * | 2010-07-21 | 2010-12-08 | 九星控股集团有限公司 | Non-vacuum smelting method of CuCrZr alloy |
| CN101613808B (en) * | 2009-07-08 | 2011-05-04 | 苏州有色金属研究院有限公司 | Non-vacuum production method for CuCrZr alloy wire rod |
| CN101760659B (en) * | 2008-12-25 | 2011-08-31 | 中国科学院兰州化学物理研究所 | Preparation method of copper-chromium intermediate alloy |
| CN102266922A (en) * | 2011-06-17 | 2011-12-07 | 九星控股集团有限公司 | Non-vacuum casting and forming method of chromium zirconium copper alloy plate for continuous casting crystallizer |
| CN101733392B (en) * | 2008-04-11 | 2013-06-12 | 中铝洛阳铜业有限公司 | Technology for casting copper alloy under non-vacuum conditions by adding zirconium |
| CN111774539A (en) * | 2020-06-08 | 2020-10-16 | 西安斯瑞先进铜合金科技有限公司 | Preparation method of non-vacuum downward-drawing copper-zirconium alloy slab ingot |
| CN112322918A (en) * | 2020-11-10 | 2021-02-05 | 宁波兴业鑫泰新型电子材料有限公司 | Method for producing large-size copper-titanium alloy ingot in non-vacuum mode |
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| DE3303170A1 (en) * | 1983-01-31 | 1984-08-02 | Siemens AG, 1000 Berlin und 8000 München | METHOD FOR PRODUCING COPPER-CHROME MELTING ALLOYS AS A CONTACT MATERIAL FOR VACUUM CIRCUIT BREAKER |
| JP2705998B2 (en) * | 1990-08-02 | 1998-01-28 | 株式会社明電舎 | Manufacturing method of electrical contact material |
| CN1033236C (en) * | 1992-12-26 | 1996-11-06 | 甘肃省机械科学研究院 | High-conductive heat-resistant cast copper alloy and its process |
| US5714117A (en) * | 1996-01-31 | 1998-02-03 | Iowa State University Research Foundation, Inc. | Air melting of Cu-Cr alloys |
| CN1366088A (en) * | 2001-09-08 | 2002-08-28 | 李倬 | Process for preparing high-strength copper alloy |
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| CN101733392B (en) * | 2008-04-11 | 2013-06-12 | 中铝洛阳铜业有限公司 | Technology for casting copper alloy under non-vacuum conditions by adding zirconium |
| CN101760659B (en) * | 2008-12-25 | 2011-08-31 | 中国科学院兰州化学物理研究所 | Preparation method of copper-chromium intermediate alloy |
| CN101613808B (en) * | 2009-07-08 | 2011-05-04 | 苏州有色金属研究院有限公司 | Non-vacuum production method for CuCrZr alloy wire rod |
| CN101906547A (en) * | 2010-07-21 | 2010-12-08 | 九星控股集团有限公司 | Non-vacuum smelting method of CuCrZr alloy |
| CN102266922A (en) * | 2011-06-17 | 2011-12-07 | 九星控股集团有限公司 | Non-vacuum casting and forming method of chromium zirconium copper alloy plate for continuous casting crystallizer |
| CN111774539A (en) * | 2020-06-08 | 2020-10-16 | 西安斯瑞先进铜合金科技有限公司 | Preparation method of non-vacuum downward-drawing copper-zirconium alloy slab ingot |
| CN111774539B (en) * | 2020-06-08 | 2021-10-29 | 西安斯瑞先进铜合金科技有限公司 | Preparation method of non-vacuum downward-drawing copper-zirconium alloy slab ingot |
| CN112322918A (en) * | 2020-11-10 | 2021-02-05 | 宁波兴业鑫泰新型电子材料有限公司 | Method for producing large-size copper-titanium alloy ingot in non-vacuum mode |
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