CN109402412A - A method of high strength copper alloy is prepared using electroslag smelting casting - Google Patents
A method of high strength copper alloy is prepared using electroslag smelting casting Download PDFInfo
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- CN109402412A CN109402412A CN201811634985.8A CN201811634985A CN109402412A CN 109402412 A CN109402412 A CN 109402412A CN 201811634985 A CN201811634985 A CN 201811634985A CN 109402412 A CN109402412 A CN 109402412A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/16—Remelting metals
- C22B9/18—Electroslag remelting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C22/00—Alloys based on manganese
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- 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
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- 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
- C22C9/01—Alloys based on copper with aluminium as the next major constituent
Abstract
The invention discloses a kind of methods for preparing high strength copper alloy using electroslag smelting casting, first, electrode bar is prepared according to copper alloy compositions, it is placed in crystallizer, powers on, melt side below in voltage 95-100V, electric current 2-2.5kA condition and add slag charge, until after the completion of slag charge addition, in voltage 95-100V, electric current 1.5-2.5kA condition remelting 10-30min, electric current is then promoted to 2.5-3kA melting 3-5min, copper alloy is made in cooling ingot.The present invention prepares copper alloy by using electroslag smelting casting, and not only copper alloy crystal grain refinement, field trash are few, and effectively increases the tensile strength of copper alloy, toughness plasticity, while improving alloy corrosion resistance and damping and amortization；In addition, this method process flow is short, easy to operate, production cost is low, and adaptability is good.
Description
Technical field
The invention belongs to copper alloy preparation fields, more particularly to the method for preparing high strength copper alloy using electroslag smelting casting.
Background technique
Often incorporation engineering needs to propose additional requirement, such as ship to corrosion resistance, wearability and conductibility high strength copper alloy
Oceangoing ship propeller high-strength corrosion-resisting Cu alloy material, the axle sleeve of winch, the worm gear of bearing shell and gearbox, worm screw use high-strength
Spend wear-resistant copper alloy, the pigtail splice high-intensity high-conductivity copper alloy of steam turbine generator.The production master of above-mentioned copper alloy products
Casting and forming is relied on, the optimization that heat treatment process realizes alloy comprehensive performance is aided with.Refining side in alloy product production process
Method is more single, the isolation of gas and pollutant is generally realized by the method covered to metal bath surface, and molten in metal
Refining agent is added in body to realize the refining of alloy.But this method production efficiency is low and refining effect is limited, so as to cause alloy
Product quality is not good enough, influences the performance of alloy material performance.Therefore, it now needs a kind of to prepare high high-quality of comprehensive performance
The method of copper alloy products.
Summary of the invention
Goal of the invention: it is high using electroslag smelting casting preparation intensity that the object of the present invention is to provide a kind of, have both it is wear-resisting, anti-corrosion,
The preparation method of damping and conductive copper alloy.
Technical solution: the method that the present invention uses electroslag smelting casting to prepare high strength copper alloy includes the following steps:
(1) electrode bar is prepared according to copper alloy compositions, be placed in crystallizer, powered on, in voltage 95-100V, electric current
2-2.5kA condition melts side below and adds slag charge, until after the completion of slag charge addition, in voltage 95-100V, electric current 1.5-2.5kA item
Part remelting 10-30min；Wherein, the mass ratio of the slag charge and copper alloy is (0.03-0.1): 1, the slag charge Zhan being added every time is total
The 10-15% of slag charge；
(2) after promoting electric current to 2.5-3kA melting 3-5min, copper alloy is made in cooling ingot.
The present invention prepares copper alloy by electroslag remelting, can not only eliminate the existing oxidation folder of master alloy material internal
Miscellaneous, gas and objectionable impurities elements are implemented to purify to material；Master alloy material internal can be eliminated simultaneously, and there are Susongs, stomata
With the casting flaws such as burning into sand；Furthermore can also effectively eliminate in master alloy tissue there are biggish Dendritic TiC, column crystal, formed it is tiny
Equiax crystal.
Furtherly, copper alloy of the invention can be aluminium bronze, manganin or Kufil.Wherein, aluminium bronze
The component of alloy includes: Al 8-11%, Fe 3-5%, Y 0.01-0.05%, Cr 0.1-0.3% and surplus copper and can not keep away
The impurity exempted from.The component of manganin include: Mn 51-53%, Al 3.0-5.0%, Fe2.0-3.0%, Ni 1.5-3.0%,
V 0.05-0.15%, Zn 1.5-3.0%, B 0.05-0.1% and surplus copper and inevitable impurity.The group of Kufil
It point include: Ag 2.8-3.2%, Zr 0.4-0.6%, V 0.1-0.3%, Y 0.03-0.08% and surplus copper and inevitable
Impurity.
The present invention is by preparing aluminium bronze, manganin and Kufil combination electroslag smelting casting, and not only tension is strong
Degree is high, plastic elongation intensity is high, and alloy corrosion resistance is strong, and damping and amortization is good.Wherein, for aluminium bronze, by original
Cr and Y, the intensity and wear-resisting property that the addition of Cr can effectively refine crystal grain, improve alloy are added in material, and adding metal Y can
Alloy crystal boundary and matrix are purified, the corrosion resisting property of alloy is improved, in combination with electroslag smelting casting preparation process, and then can reduce conjunction
The remelting of golden principal component aluminium is lost；For manganin, by adding V and B in the feed, the addition of V can kept
It can be improved the damping capacity of alloy under conditions of alloy strength index is constant, addition metal B has purification alloy crystal boundary and base
The effect of body, and energy thinning microstructure crystal grain, and the boride remained in metallic matrix has the function of solution strengthening, in combination with
Electroslag smelting casting preparation process, and then slag system is able to ascend to the refining effect of master alloy；For Kufil, by the feed
V and Y is added, addition metal V can refine crystal grain, promote the wear-resisting property of alloy, and addition metal Y can purify alloy crystal boundary and base
Body improves the electric conductivity of alloy, and the intensity of alloy is improved by remaining intermetallic compound containing Y, molten in combination with electroslag
Preparation process is cast, and then can reduce the remelting loss of active metallic element zirconium in alloy.
Furtherly, slag charge of the invention can be NaF-CaF2-Al2O3Ternary slag system, CaF2- NaF binary slag system,
Na3AlF6-CaF2- NaF ternary slag system or NaF-CaF2-Al2O3-MnO2Quaternary slag system.Wherein, NaF-CaF2-Al2O3Ternary slag
CaF in system227-70%, NaF 23-70%, Al2O33-7%.CaF2CaF in-NaF binary slag system250-65%, NaF 35-
50%.Na3AlF6-CaF2Na in-NaF ternary slag system3AlF65-15%, CaF230-45%, NaF 50-65%.NaF-CaF2-
Al2O3-MnO2NaF50-60%, CaF in quaternary slag system235-40%, Al2O32-6%, MnO20.5-4%.
The utility model has the advantages that compared with prior art, remarkable advantage of the invention are as follows: prepare copper by using electroslag smelting casting and close
Gold, not only copper alloy crystal grain refinement, field trash are few, and effectively increase the tensile strength of copper alloy, plastic elongation intensity, simultaneously
Improve alloy corrosion resistance and damping and amortization；In addition, this method process flow is short, easy to operate, production cost is low, adaptability
It is good.
Detailed description of the invention
Fig. 1 is the metallographic microscope using the aluminium bronze of existing method of smelting preparation；
Fig. 2 is the metallographic microscope of aluminium bronze prepared by the present invention；
Fig. 3 is the metallographic microscope using the manganin of existing method of smelting preparation；
Fig. 4 is the metallographic microscope of manganin prepared by the present invention；
Fig. 5 is the metallographic microscope using the Kufil of existing method of smelting preparation；
Fig. 6 is the metallographic microscope of Kufil prepared by the present invention.
Specific embodiment
Below with reference to embodiment, further details of the technical solution of the present invention.
1 aluminium bronze of embodiment
Included the following steps: using the method that electroslag smelting casting prepares aluminium bronze
(1) electrode bar is prepared according to aluminium bronze component, using monopole electroslag, is put between crystallizer and bottom water case
Annular asbestos pad is set, striking agent CaC/TiO is put into, electrode bar and dummy electrode center line ajusts direct join, adjustment electrode is always
It is maintained at crystallizer center, opens recirculated cooling water；
(2) electrode bar is directed at crystallizer center, rapid decrease electrode, when electrode lower end is electric close to connecting when striking agent
Source, descending at slow speed melt side in voltage 95-100V, electric current 2-2.5kA condition below and add slag charge, until slag charge addition is completed；Its
In, the mass ratio of slag charge and aluminium bronze is 0.03:1, the 10% of the total slag charge of slag charge Zhan being added every time；
(3) after the completion of slag charge addition, remelting 17min under the conditions of voltage 95-100V, electric current 1.5-2.5kA；
(4) after promoting electric current to 2.5-3kA melting 4min, aluminium bronze ingot casting is made in water cooling 20-30min.
Aluminium bronze ingot casting prepared by the embodiment carries out composition detection, and the result of acquisition is as shown in table 1 below.The present invention adopts
Slag charge is as shown in table 2 below.
1 aluminium bronze constituent content of table
| Component | Al | Fe | Y | Cr | Copper | Impurity |
| Content/% | 8-11 | 3-5 | 0.01-0.05 | 0.1-0.3 | Surplus | 0.5 |
2 slag system constituent content of table
| Component | NaF | CaF2 | Al2O3 |
| Content/% | 60 | 35 | 5 |
Comparative example 1
Aluminium bronze is prepared using existing method of smelting, it is specific as follows shown.
The preparation method of the aluminium bronze of the comparative example includes the following steps:
Aluminium bronze is prepared using existing Medium frequency induction method of smelting, is specifically comprised the following steps:
(1) alloy raw material and cryolite are added in the intermediate frequency furnace of graphite crucible furnace lining；
(2) electrified regulation melts alloy material and is stirred until homogeneous by hand；
(3) it is kept the temperature at 1250 DEG C, refining 20min, then skims, is poured into solidification forming in sand mo(u)ld.
Aluminium bronze prepared by embodiment 1 and comparative example 1 carries out performance detection, and the result of acquisition is as shown in table 3 below.
Aluminium bronze prepared by the embodiment 1 and comparative example 1 carries out structural characterization, shown in the result of acquisition following Fig. 1 and Fig. 2.
The performance table for the aluminium bronze that 3 embodiment 1 of table is prepared with comparative example 1
By table 3 it is found that the present invention use electroslag smelting casting preparation aluminium bronze, not only tensile strength, yield strength,
Plastic elongation intensity improves, and hardness improves, while corrosion resistance effectively improves.In combination with Fig. 1 and Fig. 2 it is found that existing
The aluminium bronze microscopic structure of founding preparation is Dendritic TiC and there are Micro Inclusions, and aluminium bronze prepared by the present invention is micro-
Tissue is equiax crystal and matrix is purified, and the corrosion resistance and intensity index of alloy material are obviously improved.
2 manganin of embodiment
Included the following steps: using the method that electroslag smelting casting prepares manganin
(1) electrode bar is prepared according to manganin component, using monopole electroslag, is placed between crystallizer and bottom water case
Annular asbestos pad is put into striking agent CaC/TiO, electrode bar and dummy electrode center line ajusts direct join, and adjustment electrode is protected always
Heart position in a crystallizer is held, recirculated cooling water is opened；
(2) electrode bar is directed at crystallizer center, rapid decrease electrode, when electrode lower end is electric close to connecting when striking agent
Source, descending at slow speed melt side in voltage 95-100V, electric current 2-2.5kA condition below and add slag charge, until slag charge addition is completed；It should
In embodiment the mass ratio of slag charge and manganin be 0.06:1, the 10% of the total slag charge of slag charge Zhan being added every time；
(3) after the completion of slag charge addition, remelting 20min under the conditions of voltage 95-100V, electric current 1.5-2.5kA；
(4) it promotes electric current and manganin ingot casting is made to 2.5-3kA melting 5min, water cooling 20-30min.
Manganin ingot casting prepared by the embodiment carries out composition detection, and the result of acquisition is as shown in table 4 below.The present invention
The slag charge of use is as shown in table 5 below.
4 manganin constituent content of table
5 slag system constituent content of table
| Component | NaF | CaF2 | Al2O3 | MnO2 |
| Content/% | 60 | 35 | 2 | 3 |
The preparation method of the manganin of the embodiment includes the following steps:
Comparative example 2
Manganin is prepared using existing Medium frequency induction method of smelting, is specifically comprised the following steps:
(1) alloy raw material and cryolite are added in the intermediate frequency furnace of magnesia furnace lining；
(2) electrified regulation melts alloy material and is stirred until homogeneous by hand；
(3) it is kept the temperature at 1380 DEG C, refining 20min, then skims, is poured into solidification forming in sand mo(u)ld.
Manganin prepared by embodiment 2 and comparative example 2 carries out performance detection, and the result of acquisition is as shown in table 6 below.It will
Manganin prepared by embodiment 2 and comparative example 2 carries out structural characterization, shown in the result of acquisition following Fig. 3 and Fig. 4.
The performance table for the manganin that 6 embodiment 2 of table is prepared with comparative example 2
By table 6 it is found that the present invention uses the manganin of electroslag smelting casting preparation, not only tensile strength, yield strength, modeling
Property extension strength improve, and hardness improve, while damping capacity improve.In combination with Fig. 3 and Fig. 4 it is found that existing founding
The defects of manganin microscopic structure of preparation is coarse Dendritic TiC, field trash uniform there are tissue odds, it is prepared by the present invention
Manganin microscopic structure is that tiny Dendritic TiC, matrix be pure, even tissue, and the corrosion resistance and intensity index of alloy material have aobvious
It writes and is promoted.
3 Kufil of embodiment
(1) electrode bar is prepared according to Kufil component, using monopole electroslag, is placed between crystallizer and bottom water case
Annular asbestos pad is put into striking agent CaC/TiO, electrode bar and dummy electrode center line ajusts direct join, and adjustment electrode is protected always
Heart position in a crystallizer is held, recirculated cooling water is opened；
(2) electrode bar is directed at crystallizer center, rapid decrease electrode, when electrode lower end is electric close to connecting when striking agent
Source, descending at slow speed melt side in voltage 95-100V, electric current 2-2.5kA condition below and add slag charge, until slag charge addition is completed；It should
In embodiment the mass ratio of slag charge and Kufil be 0.1:1, the 15% of the total slag charge of slag charge Zhan being added every time；
(3) after the completion of slag charge addition, remelting 15min under the conditions of voltage 95-100V, electric current 1.5-2.5kA；
(4) it promotes electric current and Kufil ingot casting is made to 2.5-3kA melting 5min, water cooling 20-30min.
Kufil ingot casting prepared by the embodiment carries out composition detection, and the result of acquisition is as shown in table 7 below.The present invention
The slag charge of use is as shown in table 8 below.
7 Kufil constituent content of table
| Component | Ag | Zr | Y | V | Copper | Impurity |
| Content/% | 2.8-3.2 | 0.4-0.6 | 0.03-0.08 | 0.1-0.3 | Surplus | 0.05 |
8 slag system constituent content of table
| Component | NaF | CaF2 |
| Content/% | 65 | 35 |
Comparative example 3
Kufil is prepared using existing vacuum induction melting method, is specifically comprised the following steps:
(1) alloy raw material is added in the intermediate frequency furnace of graphite crucible and is evacuated to 5000Pa；
(2) electrified regulation melts alloy material and is evacuated to 50Pa；
(3) solidification forming in mold is poured into 1300 DEG C of heat preservations, refining 20min and then turndown.
Kufil prepared by embodiment 3 and comparative example 3 carries out performance detection, and the result of acquisition is as shown in table 9 below.It will
Kufil prepared by embodiment 3 and comparative example 3 carries out structural characterization, shown in the result of acquisition following Fig. 5 and Fig. 6.
The performance table for the Kufil that 9 embodiment 3 of table is prepared with comparative example 3
By table 3 it is found that the present invention uses the Kufil of electroslag smelting casting preparation, not only tensile strength, yield strength, modeling
Property extension strength improve, and hardness improve, while relative electric conductivity promoted.In combination with Fig. 5 and Fig. 6 it is found that existing smelter
Skill preparation Kufil coarse microstructure, there are more field trash, Kufil microscopic structure prepared by the present invention is thin
It is small, matrix is pure, even tissue, the electric conductivity and intensity index of alloy material are obviously improved.
In above-described embodiment, the time of remelting can be 10-30min, promote melting 3-5min after electric current.In addition, preparing
When aluminium bronze, the NaF-CaF of use2-Al2O3CaF in ternary slag system2It can be 27-70%, NaF can be 23-70%, Al2O3
It can be 3-7%；When preparing manganin, the NaF-CaF of use2-Al2O3-MnO2In quaternary slag system NaF can for 50-60%,
CaF2It can be 35-40%, Al2O3It can be 2-6%, MnO20.5-4%；When preparing Kufil, the CaF of use2- NaF binary
CaF in slag system2It can be 50-65%, NaF can be 35-50%.
In addition, Na also can be used when preparing aluminium bronze and manganin3AlF6-CaF2- NaF ternary slag system, should
Na3AlF6-CaF2Na in-NaF ternary slag system3AlF65-15%, CaF230-45%, NaF50-65%.
Claims (10)
1. a kind of method for preparing high strength copper alloy using electroslag smelting casting, it is characterised in that include the following steps:
(1) electrode bar is prepared according to copper alloy compositions, be placed in crystallizer, powered on, in voltage 95-100V, electric current 2-
2.5kA condition melts side below and adds slag charge, until after the completion of slag charge addition, in voltage 95-100V, electric current 1.5-2.5kA condition
Remelting 10-30min；Wherein, the mass ratio of the slag charge and copper alloy is (0.03-0.1): 1, the total slag of slag charge Zhan being added every time
The 10-15% of material；
(2) after promoting electric current to 2.5-3kA melting 3-5min, copper alloy is made in cooling ingot.
2. the method according to claim 1 for preparing high strength copper alloy using electroslag smelting casting, it is characterised in that: the copper
Alloy is aluminium bronze, manganin or Kufil.
3. the method according to claim 2 for preparing high strength copper alloy using electroslag smelting casting, it is characterised in that: the aluminium
The component of bell metal includes: Al 8-11%, Fe 3-5%, Y 0.01-0.05%, Cr 0.1-0.3% and surplus copper and not
Evitable impurity.
4. the method according to claim 1 for preparing high strength copper alloy using electroslag smelting casting, it is characterised in that: the manganese
The component of copper alloy includes: Mn 51-53%, Al 3.0-5.0%, Fe 2.0-3.0%, Ni 1.5-3.0%, V 0.05-
0.15%, Zn 1.5-3.0%, B 0.05-0.1% and surplus copper and inevitable impurity.
5. the method according to claim 1 for preparing high strength copper alloy using electroslag smelting casting, it is characterised in that: the copper
The component of silver alloy includes: Ag 2.8-3.2%, Zr 0.4-0.6%, V 0.1-0.3%, Y 0.03-0.08% and surplus copper
With inevitable impurity.
6. according to right to go 1 described in high strength copper alloy is prepared using electroslag smelting casting method, it is characterised in that: the slag
Material is NaF-CaF2-Al2O3Ternary slag system, CaF2- NaF binary slag system, Na3AlF6-CaF2- NaF ternary slag system or NaF-CaF2-
Al2O3-MnO2Quaternary slag system.
7. the method according to claim 1 for preparing high strength copper alloy using electroslag smelting casting, it is characterised in that: described
NaF-CaF2-Al2O3CaF in ternary slag system227-70%, NaF 23-70%, Al2O33-7%.
8. the method according to claim 1 for preparing high strength copper alloy using electroslag smelting casting, it is characterised in that: described
CaF2CaF in-NaF binary slag system250-65%, NaF 35-50%.
9. the method according to claim 1 for preparing high strength copper alloy using electroslag smelting casting, it is characterised in that: described
Na3AlF6-CaF2Na in-NaF ternary slag system3AlF65-15%, CaF230-45%, NaF 50-65%.
10. the method according to claim 1 for preparing high strength copper alloy using electroslag smelting casting, it is characterised in that: described
NaF-CaF2-Al2O3-MnO2NaF 50-60%, CaF in quaternary slag system235-40%, Al2O32-6%, MnO20.5-4%.
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| JPH01159339A (en) * | 1987-12-15 | 1989-06-22 | Fujikura Ltd | Bonding wire |
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| CN102485377A (en) * | 2010-12-06 | 2012-06-06 | 沈阳兴工铜业有限公司 | Preparation method of chromium-zirconium-copper cooling roll for amorphous ribbon |
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