CN113699394A - Red copper refiner, preparation method and preparation method of red copper casting blank - Google Patents

Red copper refiner, preparation method and preparation method of red copper casting blank Download PDF

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Publication number
CN113699394A
CN113699394A CN202111004382.1A CN202111004382A CN113699394A CN 113699394 A CN113699394 A CN 113699394A CN 202111004382 A CN202111004382 A CN 202111004382A CN 113699394 A CN113699394 A CN 113699394A
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refiner
red copper
copper
purity
preparing
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郑良玉
王永如
巢国辉
傅杰
欧阳好
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Ningbo Jintian Copper Group Co Ltd
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Ningbo Jintian Copper Group Co Ltd
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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
    • 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
    • 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 red copper refiner, which is characterized in that: the refiner comprises the following components in percentage by mass: 20 wt% -50 wt%, B: 1 to 7 wt%, and the balance of copper and inevitable impurities. The red copper grain refiner of the invention does not influence the conductivity of the red copper, does not reduce the copper content, and the addition of the refiner does not influence the fluidity of the melt, mainly because the Ca element has strong activity, can be used as a deoxidizer of the copper, can improve the purity of the copper alloy melt, and then forms a high-melting-point compound with other impurities, can be used as a nucleation core, and refines grains; the addition of the element B mainly lies in that the element B is easy to enrich at a crystal boundary, thereby influencing the diffusion of solute atoms at the front edge of a solidification interface and inhibiting the growth of crystal grains. Ca and B act together to refine red copper grains.

Description

Red copper refiner, preparation method and preparation method of red copper casting blank
Technical Field
The invention belongs to the technical field of copper alloy, and particularly relates to a red copper refiner, a preparation method and a preparation method of a red copper casting blank.
Background
The high-purity red copper (the copper content is higher than 99.95%) has a large heat conductivity coefficient, so that the solidification speed is high in the horizontal continuous casting process, the casting blank structure is a columnar crystal structure, the integral crystal grains are large, the upper surface cooling capacity and the lower surface cooling capacity of a crystallizer are small and large due to the horizontal continuous casting process, the casting blank structure is obviously layered, the size difference of the crystal grains of the upper structure and the lower structure is large, cracks are easy to appear at the positions where the large crystal grains and the small crystal grains are connected during the subsequent rolling, and the quality of a finished product is seriously influenced.
In order to obtain a structure with uniform structure and fine grains, a refiner is preferably added into the melt, but the conductivity of the high-purity red copper cannot be influenced. At present, the grain refiner commonly used in copper alloy is a rare earth refiner mainly containing Al, Ti, B and rare earth elements or a modified refiner, for example, in patent CN201910802640.7, the combination of Fe-Si alloy, KBF4, carbonate and manganese is utilized to refine the structure, the refiners are often used for refining brass structure, but for high-purity red copper, the addition of Ti, Si, Fe and other elements in the refiner seriously reduces the conductivity of the red copper, and then the melt viscosity is high, and the cast blank is easy to crack. Therefore, no grain refiner for high-purity red copper exists in the industry at present.
Disclosure of Invention
The invention aims to solve the first technical problem of providing a refiner capable of refining the grain structure of high-purity red copper without influencing the conductivity.
The technical scheme adopted by the invention for solving the first technical problem is as follows: a high-purity red copper refiner is characterized in that: the refiner comprises the following components in percentage by mass: 20 wt% -50 wt%, B: 1 to 7 wt%, and the balance of copper and inevitable impurities.
In order to ensure the refining effect of the refiner, the Ca content in the refiner is at least higher than 20 percent, and the B content is higher than 1 percent. When the Ca content exceeds 50%, the refiner is very easily oxidized and the stability is not high, and when the Ca content exceeds 50% and the B content exceeds 7%, the degree of alloying is reduced and the refining effect is deteriorated.
The second technical problem to be solved by the invention is to provide a preparation method of the high-purity red copper refiner.
The technical scheme adopted by the invention for solving the second technical problem is as follows: a preparation method of a high-purity red copper refiner is characterized by comprising the following steps: the preparation method comprises the following preparation steps:
1) preparing materials: preparing an electrolytic plate, a boron ingot and calcium according to the proportion of each element, wherein the purity of the boron ingot and the purity of the calcium are more than 99%, and the purity of the electrolytic plate is more than 99.99%;
2) smelting: putting the electrolytic plate into a high-purity graphite crucible of a vacuum smelting furnace, and vacuumizing to 10 DEG-3Electrifying to melt after the pressure is lower than Pa until the electrolytic plate is melted to obtain copper liquid, and controlling the temperature of the copper liquid to be 1200-1400 ℃; introducing Ar gas into a vacuum furnace, controlling the pressure in the vacuum furnace to be 0.5-1 atmospheric pressure, adding a boron ingot, and adding calcium after the boron ingot is molten;
3) casting: and after all the ingredients are melted, preserving the heat for 0.5-2 h, and pouring into an iron mold to obtain the refiner.
Preferably, in the step 2), the purity of the Ar gas is 99.999%.
The third technical problem to be solved by the invention is to provide a preparation method of a red copper casting blank.
The technical scheme adopted by the invention for solving the third technical problem is as follows: a preparation method of a red copper casting blank is characterized by comprising the following steps: the preparation method comprises the following preparation steps:
1) preparing materials: an electrolytic plate, a refiner of claim 2;
2) smelting: smelting: melting the electrolytic plate, pressing the refiner into the melt by using a high-purity graphite bell jar when the melt temperature is 1160-1180 ℃, wherein the pressing depth is more than 20cm, and the retention time is more than 10 minutes; adding 40-100 g of a refiner into each ton of melt;
3) casting: and horizontally continuously casting to obtain a casting blank.
Melting the electrolytic plate, when the melt temperature is 1160-1180 ℃, pressing the refiner into the melt by using a high-purity graphite bell jar because the density of the refiner is less than that of copper, and then keeping the pressing depth of the refiner to be more than 20cm for more than 10 minutes in order to ensure the use effect and the uniform diffusion; at least 40g of refiner is added into each ton of melt to ensure the refining effect, but the refiner does not exceed 100g so as not to influence the conductivity;
and preventing the oxidation in the feeding process, preferably, in the step 1), in order to ensure that the grain diameter of the refiner is below 1cm, the refiner is coated with T2 red copper.
Preferably, in the step 3), the refiner is added every 1h in the step 3), and the addition amount is (n/t) × (40-100 g), wherein n is the amount of the cast slab for 1h, and the unit of the amount of the cast slab is t.
Preferably, the microstructure of the red copper ingot is 1cm in cross section2The number of the crystal grains in the crystal grain is 80-150.
Preferably, the number of crystal grains passing through the thickness direction in a longitudinal section of the microstructure of the red copper cast slab is 20 to 40.
Compared with the prior art, the invention has the advantages that: the red copper grain refiner of the invention does not influence the conductivity of high-purity red copper, does not reduce the copper content, and the addition of the refiner does not influence the fluidity of the melt, mainly because Ca element has strong activity, can be used as a deoxidizer of copper, can improve the purity of the copper alloy melt, and then forms a high-melting point compound with other impurities, can be used as a nucleation core to refine grains; the addition of the element B mainly lies in that the element B is easy to enrich at a crystal boundary, thereby influencing the diffusion of solute atoms at the front edge of a solidification interface and inhibiting the growth of crystal grains. The Ca and the B act together to refine red copper crystal grains, and the average grain size is below 2 mm.
Drawings
FIG. 1 is a metallographic structure of a cross section of example 1 of the present invention (photographed ratio 1: 1);
FIG. 2 is a metallographic structure of a longitudinal section of example 1 of the present invention (photographing ratio 1: 1);
FIG. 3 is a metallographic structure of a cross section of comparative example 1 of the present invention (photographed ratio 1: 1);
FIG. 4 is a metallographic structure of a longitudinal section of comparative example 1 of the present invention (photographed ratio 1: 1).
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Example 1
The high-purity red copper refiner comprises the following components in percentage by mass: ca: 20 wt%, B: 5 wt%, the balance being copper.
The preparation of the refiner comprises the following preparation steps:
1) preparing materials: preparing an electrolytic plate, a boron ingot and calcium according to the proportion of each element, wherein the purity of the boron ingot and the purity of the calcium are more than 99%, and the purity of the electrolytic plate is more than 99.99%;
2) smelting: putting the electrolytic plate into a high-purity graphite crucible of a vacuum smelting furnace, and vacuumizing to 10 DEG-3Electrifying and melting after the pressure is lower than Pa until the electrolytic plate is melted to obtain copper liquid, and controlling the temperature of the copper liquid at 1200 ℃; introducing Ar gas with the purity of 99.999 percent into a vacuum furnace, controlling the pressure in the furnace to be 0.5 atmospheric pressure, adding boron ingots, and adding calcium after the boron ingots are melted;
4) casting: and (3) after all the ingredients are melted, preserving the heat for 1h, and pouring into an iron mold to obtain the refiner.
The preparation method of the red copper comprises the following preparation steps:
1) preparing materials: an electrolytic plate and a refiner;
2) smelting: melting the electrolytic plate, pressing the refiner into the melt by using a high-purity graphite bell jar when the melt temperature is 1160 ℃, wherein the pressing depth is 25cm, and the retention time is 15 minutes; adding 100g of refiner into each ton of melt; the grain size of the refiner is below 1cm, and the refiner is coated with T2 red copper.
3) Casting: and horizontally continuously casting to obtain a casting blank, wherein the section specification of the casting blank is 20mm by 630 mm. And adding the refiner every 1h, wherein the adding amount is 50g, and the adding amount is 0.5t per 1h of the casting blank, namely 50g, and is 0.5 ﹡ 100 g.
Example 2
The red copper refiner of the embodiment comprises the following components in percentage by mass: ca: 30 wt%, B: 5 wt%, the balance being copper.
The preparation of the refiner comprises the following preparation steps:
1) preparing materials: preparing an electrolytic plate, a boron ingot and calcium according to the proportion of each element, wherein the purity of the boron ingot and the purity of the calcium are more than 99%, and the purity of the electrolytic plate is more than 99.99%;
2) smelting: putting the electrolytic plate into a high-purity graphite crucible of a vacuum smelting furnace, and vacuumizing to 10 DEG-3Electrifying and melting after the pressure is lower than Pa until the electrolytic plate is melted to obtain copper liquid, and controlling the temperature of the copper liquid at 1300 ℃; introducing Ar gas with the purity of 99.999 percent into a vacuum furnace, controlling the pressure in the furnace to be 1 atmosphere, adding boron ingots, and adding calcium after the boron ingots are melted;
4) casting: and (3) after all the ingredients are melted, preserving the heat for 2 hours, and pouring into an iron mold to obtain the refiner.
The preparation method of the red copper comprises the following preparation steps:
1) preparing materials: an electrolytic plate and a refiner;
2) smelting: melting the electrolytic plate, pressing the refiner into the melt by using a high-purity graphite bell jar when the temperature of the melt is 1180 ℃, wherein the pressing depth is 20cm, and the retention time is 10 minutes; adding 50g of refiner into each ton of melt; the grain size of the refiner is below 1cm, and the refiner is coated with T2 red copper.
3) Casting: and horizontally continuously casting to obtain a casting blank, wherein the section specification of the casting blank is 20mm by 630 mm. And adding the refiner every 1h, wherein the adding amount is 30g, and the adding amount is 0.6t per 1h of the casting blank and is 30g which is 0.6 ﹡ 50 g.
Example 3
The red copper refiner of the embodiment comprises the following components in percentage by mass: ca: 40 wt%, B: 7 wt%, the balance being copper.
The preparation of the refiner comprises the following preparation steps:
1) preparing materials: preparing an electrolytic plate, a boron ingot and calcium according to the proportion of each element, wherein the purity of the boron ingot and the purity of the calcium are more than 99%, and the purity of the electrolytic plate is more than 99.99%;
2) smelting: putting the electrolytic plate into a high-purity graphite crucible of a vacuum smelting furnace, and vacuumizing to 10 DEG-3Electrifying to melt after Pa is lower than Pa until the electrolytic plate is melted to obtain copper liquid, and controlling copperThe temperature of the liquid is 1400 ℃; introducing Ar gas with the purity of 99.999 percent into a vacuum furnace, controlling the pressure in the furnace to be 1 atmosphere, adding boron ingots, and adding calcium after the boron ingots are melted;
4) casting: and (3) after all the ingredients are melted, preserving the heat for 1h, and pouring into an iron mold to obtain the refiner.
The preparation method of the red copper comprises the following preparation steps:
1) preparing materials: an electrolytic plate and a refiner;
2) smelting: melting the electrolytic plate, pressing the refiner into the melt by using a high-purity graphite bell jar when the temperature of the melt is 1180 ℃, wherein the pressing depth is 30cm, and the retention time is 20 minutes; adding 60g of refiner into each ton of melt; the grain size of the refiner is below 1cm, and the refiner is coated with T2 red copper.
3) Casting: and horizontally continuously casting to obtain a casting blank, wherein the section specification of the casting blank is 20mm by 630 mm. And adding the refiner every 1h, wherein the adding amount is 50g, and the adding amount is 0.5t per 1h of the casting blank, namely 50g, and is 0.5 ﹡ 100 g.
The comparative example differs from the examples in that no refiner is added during the casting of red copper.
And (3) detecting the content of Cu: according to GB/T5121.1-2008, the chemical analysis method of copper and copper alloy is provided.
Conductivity detection: according to GB/T32791-2016, a method for eddy current testing of the conductivity of copper and copper alloys.
And (3) detecting the grain size: refer to the intercept method in the average grain size test method YS/T347-2004 for copper and copper alloys. The specific method comprises the following steps: drawing a rectangular frame of 1cm by 1cm on the cross section2The number of dies contained within the area (including the dies through which the frame passes); and drawing a line on the longitudinal section along the thickness direction, and counting the number of crystal grains penetrated by the drawn line.
TABLE 1 conductivity and grain size of inventive and comparative examples
Figure BDA0003236695070000051

Claims (8)

1. A red copper refiner is characterized in that: the refiner comprises the following components in percentage by mass: 20 wt% -50 wt%, B: 1 to 7 wt%, and the balance of copper and inevitable impurities.
2. A method for preparing a copper refiner according to claim 1, characterized in that: the preparation method comprises the following preparation steps:
1) preparing materials: preparing an electrolytic plate, a boron ingot and calcium according to the proportion of each element, wherein the purity of the boron ingot and the purity of the calcium are more than 99%, and the purity of the electrolytic plate is more than 99.99%;
2) smelting: putting the electrolytic plate into a high-purity graphite crucible of a vacuum smelting furnace, and vacuumizing to 10 DEG-3Electrifying to melt after the pressure is lower than Pa until the electrolytic plate is melted to obtain copper liquid, and controlling the temperature of the copper liquid to be 1200-1400 ℃; introducing Ar gas into a vacuum furnace, controlling the pressure in the vacuum furnace to be 0.5-1 atmospheric pressure, adding a boron ingot, and adding calcium after the boron ingot is molten;
3) casting: and after all the ingredients are melted, preserving the heat for 0.5-2 h, and pouring into an iron mold to obtain the refiner.
3. The method for preparing a copper refiner according to claim 2, characterized in that: in the step 2), the purity of Ar gas is 99.999%.
4. A preparation method of a red copper casting blank is characterized by comprising the following steps: the preparation method comprises the following preparation steps:
1) preparing materials: an electrolytic plate, a refiner of claim 2;
2) smelting: melting the electrolytic plate, pressing the refiner into the melt by using a high-purity graphite bell jar when the melt temperature is 1160-1180 ℃, wherein the pressing depth is more than 20cm, and the retention time is more than 10 minutes; adding 40-100 g of a refiner into each ton of melt;
3) casting: and horizontally continuously casting to obtain a casting blank.
5. The method for preparing the red copper ingot blank according to claim 4, wherein: in the step 1), the grain diameter of the refiner is below 1cm, and the refiner is coated by T2 red copper.
6. The method for preparing the red copper ingot blank according to claim 4, wherein: and in the step 3), the refiner is supplemented every 1h, wherein the supplement amount is (n/t) x (40-100 g), n is the amount of the casting blank for 1h, and the unit of the amount of the casting blank for drawing is t.
7. The method for preparing the red copper ingot blank according to claim 4, wherein: the microstructure of the red copper casting blank has a cross section of 1cm2The number of the crystal grains in the crystal grain is 80-150.
8. The method for preparing the red copper ingot blank according to claim 4, wherein: in the microstructure of the red copper casting blank, the number of crystal grains passing through the longitudinal section along the thickness direction is 20-40.
CN202111004382.1A 2021-08-30 2021-08-30 Red copper refiner, preparation method and preparation method of red copper casting blank Pending CN113699394A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3627282A1 (en) * 1986-08-12 1988-02-18 Sueddeutsche Kalkstickstoff Alloy for refining the grain of copper materials
CN101437967A (en) * 2005-04-19 2009-05-20 斯特恩利奇公司 Method for adding boron to metal alloys
CN102912154A (en) * 2012-11-02 2013-02-06 南阳市汇森精密仪器铸造有限公司 Melting process for increasing conductivity of red copper
CN107164648A (en) * 2017-05-10 2017-09-15 宁波金田铜业(集团)股份有限公司 The grain refiner and its preparation and application of a kind of environmentally friendly brass
CN112322924A (en) * 2020-10-16 2021-02-05 中南大学 Oxygen-free copper, preparation method and application

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3627282A1 (en) * 1986-08-12 1988-02-18 Sueddeutsche Kalkstickstoff Alloy for refining the grain of copper materials
CN101437967A (en) * 2005-04-19 2009-05-20 斯特恩利奇公司 Method for adding boron to metal alloys
CN102912154A (en) * 2012-11-02 2013-02-06 南阳市汇森精密仪器铸造有限公司 Melting process for increasing conductivity of red copper
CN107164648A (en) * 2017-05-10 2017-09-15 宁波金田铜业(集团)股份有限公司 The grain refiner and its preparation and application of a kind of environmentally friendly brass
CN112322924A (en) * 2020-10-16 2021-02-05 中南大学 Oxygen-free copper, preparation method and application

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Application publication date: 20211126