CN108977679B - Covering agent for chromium zirconium copper smelting and preparation and use methods thereof - Google Patents
Covering agent for chromium zirconium copper smelting and preparation and use methods thereof Download PDFInfo
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- CN108977679B CN108977679B CN201810814454.0A CN201810814454A CN108977679B CN 108977679 B CN108977679 B CN 108977679B CN 201810814454 A CN201810814454 A CN 201810814454A CN 108977679 B CN108977679 B CN 108977679B
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- 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
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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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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Abstract
The invention discloses a covering agent for chromium zirconium copper smelting and a preparation method and a use method thereof, wherein the covering agent mainly comprises carbonate, silicate, villiaumite, borate, oxide and the like, and the covering agent comprises the following components in percentage by mass: 40-80% of silicate, 10-30% of carbonate, 5-20% of fluoride, 5-8% of chloride, 5-10% of boron salt and 0-5% of oxide. The preparation process of the covering agent for smelting chromium, zirconium and copper is simple, environment-friendly and pollution-free; when the alloy is used for chromium-zirconium-copper smelting, the burning loss of zirconium in an ingot can be reduced to 30-40% from the original 80-100% after heat preservation for 30min, the use is convenient, the effect is very obvious, and the problem of air holes in the ingot due to air suction of a melt is solved.
Description
Technical Field
The invention belongs to the field of chemical metallurgy, relates to a covering agent for high-strength high-conductivity alloy smelting, and particularly relates to a covering agent for chromium-zirconium-copper smelting and a preparation method and a use method thereof.
Background
The chromium-zirconium-copper alloy belongs to one of high-strength and high-conductivity alloys, has good electrical conductivity, thermal conductivity, high hardness, wear resistance, explosion resistance, crack resistance and softening temperature, less electrode loss during welding, high welding speed and low total welding cost, is widely applied to various materials for welding, contact tips, switch contacts, mold blocks and welding auxiliary devices in the mechanical industries of automobiles, motorcycles and the like, but in the casting process under a non-vacuum state, the burning loss of zirconium is particularly serious, so that the smelted casting blank is frequently generated, the components are not uniform, even in the later stage of casting, no zirconium exists, the problem of gas suction also exists in the casting process, the casting blank has serious central gas holes, the casting blank is directly scrapped, and the problem of gas suction of a melt and the central gas holes can be prevented at the same time.
The chromium-zirconium-copper alloy is mainly used for welding electrodes, and the production process comprises the steps of fusion casting, extrusion, solid solution, stretching, aging, stretching, sizing, fine inspection and packaging. The casting has the highest requirement on the melting and smelting of chromium, zirconium and copper, and not only has strict component requirements (especially on zirconium), but also the casting blank can not generate air holes and impurities, so that the material is ensured to have good strong hardness, electric conductivity and high-temperature softening performance. In view of this, it is important to develop a covering agent for chromium zirconium copper and a method for using the same.
Disclosure of Invention
The invention mainly aims to provide the covering agent for chromium-zirconium-copper smelting, which has the advantages of good effect, simple preparation process and environmental protection, and the preparation method and the use method thereof.
The invention firstly provides a covering agent for smelting chromium, zirconium and copper, which mainly comprises carbonate, silicate, villaumite, chloride, borate, oxide and the like, wherein the silicate is mainly Na2SiO3，CaSiO3Etc. (glass); the carbonate is mainly Na2CO3，CaCO3，MgCO3Etc.; the fluoride salt is mainly NaAlF6，CaF2Etc.; the chloride salt mainly comprises NaCl, KCl and the like; the boron salt is mainly Na2B4O7(ii) a The oxide being predominantly SiO2。
The invention also provides a preparation method of the covering agent for chromium-zirconium-copper smelting, which is prepared by mixing the raw materials of carbonate, silicate, villaumite, chloride, borate and oxide according to the proportion and uniformly stirring.
The invention also provides a use method of the covering agent for chromium-zirconium-copper smelting, after copper is melted in a non-vacuum state, the covering agent is added, so that the burning loss of zirconium in an ingot can be greatly reduced, the effect is very obvious, and the problem of air holes of a casting blank caused by air suction of a melt is solved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the first aspect of the invention provides a covering agent for chromium zirconium copper smelting, which comprises the following components in percentage by mass: 40-80% of silicate, 10-30% of carbonate, 5-20% of fluoride, 5-8% of chloride, 5-10% of boron salt and 0-5% of oxide.
Further, in the covering agent for smelting chromium-zirconium-copper, the covering agent comprises the following components in percentage by mass: 55-80% of silicate, 10-20% of carbonate, 10-20% of fluoride, 5-7% of chloride, 5-7% of boron salt and 0-4% of oxide.
Further preferably, in the covering agent for chromium zirconium copper smelting, the silicate is Na as a main component2SiO3、CaSiO3The bulk silicate glass of (1).
Further preferably, in the covering agent for chromium zirconium copper smelting, the carbonate is selected from Na2CO3、CaCO3、MgCO3Several or several of them.
Further preferably, in the covering agent for chromium zirconium copper smelting, the fluorine salt is selected from NaAlF6、CaF2One or two of them; the chloride salt is selected from one or two of NaCl and KCl.
Further preferably, in the covering agent for chromium zirconium copper smelting, the boron salt is Na2B4O7(ii) a The oxide is SiO2And the boron salt and the oxide are both in powder form.
The second aspect of the invention provides a preparation method of the covering agent for chromium-zirconium-copper smelting, which comprises the following steps:
(1) sequentially weighing carbonate, fluoride, chloride, boron salt, oxide powder and blocky silicate according to the mass ratio, and crushing blocky silicate glass into glass powder with the particle size of 10-20 mu m;
(2) sequentially adding carbonate, fluoride, chlorine salt, boron salt, oxide and glass powder into a mixing container, stirring for 5-10min at the speed of 500-700r/min, and uniformly mixing to obtain the catalyst.
The third aspect of the invention provides a method for using the covering agent for chromium-zirconium-copper smelting, which comprises the following steps:
(1) adding copper into an induction furnace for melting in a non-vacuum state, adding the covering agent as defined in any one of claims 1-5 into the molten copper, and heating the molten copper to 1280-1350 ℃;
(2) adding metal chromium into the copper liquid added with the covering agent, and preserving the heat for more than 10 min;
(3) and (3) adding a copper-zirconium intermediate alloy into the smelting liquid obtained in the step (2), and casting after complete melting.
Further, in the use method of the covering agent for chromium zirconium copper smelting, the adding amount of the covering agent in the step (1) is based on the covering copper water liquid level, and the thickness of the covering agent molten liquid level is ensured to be at least 2 mm.
Further, in the using method of the covering agent for chromium-zirconium-copper smelting, in the step (3), the temperature of the smelting liquid is controlled to be 1180-1240 ℃, and then the copper-zirconium intermediate alloy is added.
By adopting the technical scheme, compared with the prior art, the invention has the following technical effects:
the covering agent for smelting chromium, zirconium and copper provided by the invention has the advantages of simple preparation process, environmental protection and no pollution; when the alloy is used for smelting chromium, zirconium and copper, the use is convenient, the burning loss of zirconium in an ingot can be reduced to 30-40% from the original 80-100% after the alloy is used and the heat is preserved for 30min, the effect is very obvious, and the problem of air holes in a casting blank caused by air suction of a melt is solved.
Drawings
FIG. 1 is a graph showing the tendency of burning loss of Cr and Zr when the covering agent prepared in example 1 of the present invention is used in the smelting of Cr-Zr-Cu alloy;
FIG. 2 is a graph showing the tendency of the covering agent prepared in example 2 of the present invention to cause chromium-zirconium burning loss when used in chromium-zirconium-copper smelting;
FIG. 3 is a graph showing the tendency of the covering agent prepared in example 3 of the present invention to cause chromium-zirconium burnout when used in chromium-zirconium-copper smelting;
FIG. 4 is a diagram showing the burning loss tendency of chromium and zirconium in the case of using charcoal as a covering agent in chromium-zirconium-copper smelting in a comparative example of the present invention.
Detailed Description
The present invention will be described in detail and specifically with reference to the following examples to facilitate better understanding of the present invention, but the following examples do not limit the scope of the present invention.
Example 1
Selecting 65% of silicate, 15% of carbonate, 5% of fluoride, 6% of chloride, 5% of boron salt and 4% of oxide, preparing the melt covering agent according to the proportion, fully and uniformly mixing the powdery raw materials, and packaging by using a packaging bag.
In a non-vacuum state, carrying out chromium-zirconium-copper smelting in a 50kg medium frequency induction furnace, after copper is melted, adding a covering agent, simultaneously increasing the temperature to about 1300 ℃, wherein the adding amount is based on the covering copper water liquid level, the thickness of the covering agent molten liquid level is ensured to be about 2mm, simultaneously adding metal chromium, preserving the temperature for more than 10min, then reducing the voltage, controlling the temperature to 1180-1240 ℃, adding a copper-zirconium intermediate alloy, preserving the temperature, recording the burning loss change of zirconium, and the burning loss trend of chromium and zirconium is shown in figure 1.
Example 2
Selecting 70% of silicate, 10% of carbonate, 5% of fluoride, 6% of chloride, 5% of boron salt and 4% of oxide, preparing a melt covering agent according to the proportion, fully and uniformly mixing the powdery raw materials, and packaging by using a packaging bag.
In a non-vacuum state, carrying out chromium-zirconium-copper smelting in a 50kg medium frequency induction furnace, after copper is melted, adding a covering agent, simultaneously increasing the temperature to about 1300 ℃, wherein the adding amount is based on the covering copper water liquid level, the thickness of the covering agent molten liquid level is ensured to be about 2mm, simultaneously adding metal chromium, preserving the temperature for more than 10min, then reducing the voltage, controlling the temperature to 1180-1240 ℃, adding a copper-zirconium intermediate alloy, preserving the temperature, recording the burning loss change of zirconium, and the burning loss trend of chromium and zirconium is shown in figure 2.
Example 3
Selecting 75% of silicate, 5% of carbonate, 5% of fluoride, 6% of chloride, 5% of boron salt and 4% of oxide, preparing the melt covering agent according to the proportion, fully and uniformly mixing the powdery raw materials, and packaging by using a packaging bag.
In a non-vacuum state, carrying out chromium-zirconium-copper smelting in a 50kg medium frequency induction furnace, after copper is melted, adding a covering agent, simultaneously increasing the temperature to about 1300 ℃, wherein the adding amount is based on the covering copper water liquid level, the thickness of the covering agent molten liquid level is ensured to be about 2mm, simultaneously adding metal chromium, preserving the temperature for more than 10min, then reducing the voltage, controlling the temperature to 1180-1240 ℃, adding a copper-zirconium intermediate alloy, preserving the temperature, recording the burning loss change of zirconium, and the burning loss trend of chromium and zirconium is shown in figure 3.
Comparative example 1
In a non-vacuum state, carrying out chromium-zirconium-copper smelting in a 50kg intermediate frequency induction furnace, after copper is melted, only adding part of charcoal to cover, simultaneously increasing the temperature to about 1300 ℃, simultaneously adding metal chromium, preserving the temperature for more than 10min, then reducing the voltage, controlling the temperature to 1180-1240 ℃, adding a copper-zirconium intermediate alloy, preserving the temperature, and recording the burning loss change of zirconium, wherein the burning loss trend of chromium and zirconium is shown in figure 4.
As can be seen from the examples 1-3 and the comparative example, the covering agent for smelting chromium, zirconium and copper is used for smelting chromium, zirconium and copper, the heat preservation time is 30min, the burning loss of zirconium can be reduced from 80% -100% to 30% -40%, the effect is very obvious, and the defect that the casting blank has air holes due to air suction of a melt in the prior art is overcome; the covering agent provided by the invention is simple in preparation process, environment-friendly, pollution-free, convenient to use and remarkable in effect.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (4)
1. The covering agent for smelting chromium, zirconium and copper is characterized by comprising the following components in percentage by mass: 70% of silicate, 10% of carbonate, 5% of fluoride, 6% of chloride, 5% of boron salt and 4% of oxide;
the silicate is bulk silicate glass with main components of Na2SiO3 and CaSiO 3;
the carbonate is selected from one or more of Na2CO3, CaCO3 and MgCO 3;
the fluoride is selected from one or two of NaAlF6 and CaF 2;
the chloride salt is selected from one or two of NaCl and KCl;
the boron salt is Na2B4O 7; the oxide is SiO 2;
the preparation method of the covering agent for smelting chromium, zirconium and copper comprises the following steps:
(1) sequentially weighing carbonate, fluoride, chloride, boron salt, oxide powder and blocky silicate according to the mass ratio, and crushing blocky silicate glass into glass powder with the particle size of 10-20 mu m;
(2) sequentially adding carbonate, fluoride, chlorine salt, boron salt, oxide and glass powder into a mixing container, stirring for 5-10min at the speed of 500-700r/min, and uniformly mixing to obtain the catalyst.
2. The use method of the covering agent for chromium zirconium copper smelting as claimed in claim 1, characterized by comprising the following steps:
(1) adding copper into an induction furnace for melting in a non-vacuum state, adding the covering agent as claimed in claim 1 into molten copper, and heating the molten copper to 1280-1350 ℃;
(2) adding metal chromium into the copper liquid added with the covering agent, and preserving the heat for more than 10 min;
(3) and (3) adding a copper-zirconium intermediate alloy into the smelting liquid obtained in the step (2), and casting after complete melting.
3. The method for using the covering agent for chromium zirconium copper smelting as claimed in claim 2, wherein the covering agent is added in step (1) in an amount based on the covering copper water level, so as to ensure that the thickness of the covering agent molten liquid level is at least 2 mm.
4. The use method of the covering agent for chromium-zirconium-copper smelting as claimed in claim 2, wherein in the step (3), the temperature of the smelting solution is controlled to 1180-1240 ℃, and then the copper-zirconium intermediate alloy is added.
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| CN201810814454.0A CN108977679B (en) | 2018-07-23 | 2018-07-23 | Covering agent for chromium zirconium copper smelting and preparation and use methods thereof |
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| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1229857A (en) * | 1998-03-19 | 1999-09-29 | 中国船舶工业总公司第七研究院第七二五研究所 | High conductivity and heat heat resistance cast copper alloy and its prodn. method |
| CN102560182A (en) * | 2011-12-28 | 2012-07-11 | 浦瑞霆 | Method and device for smelting CuCrZr alloy in atmosphere |
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| CN1757777A (en) * | 2005-11-01 | 2006-04-12 | 邹志尚 | Antideviation and shrinkage porosity agent for uniformly softening low temperature annealing deinternal stress of cast bronze |
| CN101817066B (en) * | 2010-05-14 | 2013-02-13 | 大连理工大学 | Covering agent for smelting copper alloy |
| CN103184357B (en) * | 2011-12-29 | 2015-04-01 | 北京新北铜铝业有限责任公司 | Method of non-vacuum melting and casting copper-chromium-zirconium alloy |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1229857A (en) * | 1998-03-19 | 1999-09-29 | 中国船舶工业总公司第七研究院第七二五研究所 | High conductivity and heat heat resistance cast copper alloy and its prodn. method |
| CN102560182A (en) * | 2011-12-28 | 2012-07-11 | 浦瑞霆 | Method and device for smelting CuCrZr alloy in atmosphere |
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