CN106399728A - Smelting method for high-manganese aluminum bronze alloy - Google Patents

Abstract

The smelting method of high manganese aluminum bronze alloy disclosed by the present invention, the main steps are: furnace body treatment of intermediate frequency induction furnace and installation of gas diffusion device, design of alloy composition, preparation of raw materials and tools used in the smelting process, raw material loading and treatment, Furnace material is heated and melted, argon is passed through the bottom of the furnace, the temperature is lowered and the material is added, the composition is initially inspected, the quality of the melt is inspected, and the alloy is released from the furnace. The smelting method of the high manganese aluminum bronze alloy of the present invention can be used for the smelting of high manganese aluminum bronze ZCuAl8Mn13Fe3N i2 and ZCuAl8Mn14Fe3Ni2 alloys, can be used for the preparation of high manganese aluminum bronze standard materials, and can also be used for high manganese aluminum bronze alloys with high requirements on components and casting quality Production of products.

Description

Smelting method of high manganese aluminum bronze alloy

technical field

The invention belongs to the technical field of alloy smelting methods, in particular to a method for smelting high manganese aluminum bronze alloys.

Background technique

High-manganese aluminum bronze is a high-strength corrosion-resistant alloy with Mn and Al as the main alloying elements, and the alloy properties are strengthened by adding Fe, Ni, Zn and other metal elements. The commonly used grades are ZCuAl8Mn13Fe3Ni2 and ZCuAl8Mn14Fe3Ni2. Strength, corrosion fatigue strength and cavitation corrosion resistance, good casting performance and strong weldability, it is the main material used to prepare ship propellers all over the world.

In the traditional high-manganese-aluminum bronze smelting process, Al, Mn, Fe, and Ni are generally used as the main alloying elements, which are the control components of the alloy, and are usually added in the form of copper-manganese, copper-nickel intermediate alloys, industrial pure aluminum, and iron nails. , while Zn, Si, and Pb are used as impurity elements, and only the upper limit content is controlled. During smelting, make full use of the protective effect of the generated Al ₂ O ₃ oxide film on the alloy liquid, isolate the influence of gas in the air on the alloy liquid, reduce the stirring of the metal liquid, and avoid the inclusion of oxides; during refining, Add powdery flux for deslagging and degassing. However, this process cannot accurately control the alloying elements in the high manganese aluminum bronze, and other impurity elements will be brought in due to the influence of the quality of the intermediate alloy.

According to the smelting characteristics of non-ferrous alloys, high manganese aluminum bronze alloys are inevitably in contact with air during the smelting process, and gases such as hydrogen and oxygen in the air are easily dissolved into the molten metal, causing pore defects in castings; at the same time, the generated oxides are easily Involved in the molten metal, the formation of suspended slag stays in the molten metal, making it difficult to remove slag. In the absence of stirring, it is difficult for high-melting point metals to melt rapidly during the smelting process, and it is difficult for high-density and low-density metals to be evenly distributed in the molten metal, causing severe segregation of the chemical composition of castings. The use of powdery flux will increase the air pollution on the production site and endanger the health of the staff. More importantly, it is difficult to meet the technical requirements for some high manganese aluminum bronze products with strict requirements by using traditional smelting technology.

In the preparation process of high manganese aluminum bronze alloy reference materials, strict requirements are put forward for the alloy composition, and the seven alloy elements of Al, Mn, Fe, Ni, Zn, Si, and Pb must meet the design requirements. At the same time, defects such as pores and slag inclusions are not allowed in the prepared ingot, and the chemical composition of the ingot should be evenly distributed. The smelting of high-manganese-aluminum-bronze alloy is particularly important as the first link in the preparation process. Therefore, a new smelting process must be adopted to improve the quality of molten metal and further improve the quality of high-manganese-aluminum-bronze alloy products.

Contents of the invention

The purpose of the present invention is to provide a method for smelting high-manganese-aluminum-bronze alloys, which is especially suitable for smelting ZCuAl8Mn13Fe3Ni2 alloys and ZCuAl8Mn14Fe3Ni2 alloys, to ensure that the alloy metal liquid can meet the requirements for the preparation of standard substances, and to solve the problem that the content of alloy components cannot be accurately controlled under traditional techniques , while reducing the slag and gas content in the molten metal.

The technical scheme adopted in the present invention is that the smelting method of high manganese aluminum bronze alloy is specifically implemented according to the following steps:

Step 1. First process the furnace body of the intermediate frequency induction furnace; then install a gas diffusion device at the center of the hearth bottom of the intermediate frequency induction furnace; finally add the cast iron material to the intermediate frequency induction furnace for baking;

Step 2. After step 1 is completed, design the alloy composition according to the composition of the ZCuAl8Mn13Fe3Ni2 alloy or ZCuAl8Mn14Fe3Ni2 alloy to be smelted;

The content range of ZCuAl8Mn13Fe3Ni2 alloy elements is: Al: 7.00wt.% ~ 8.50wt.%, Mn: 11.50wt.% ~ 14.00wt.%, Fe: 2.50wt.% ~ 4.00wt.%, Ni: 1.80wt.%. ～2.50wt.%, Zn: <0.5wt.%, Si: ≤0.15wt.%, Pb: ≤0.02wt.%, the rest are Cu, N, H, O, and the sum of the weight percentages of each component is 100%. ;

The content range of ZCuAl8Mn14Fe3Ni2 alloy elements is: Al: 7.80wt.% ~ 8.80wt.%, Mn: 13.50wt.% ~ 15.00wt.%, Fe: 2.80wt.% ~ 4.00wt.%, Ni: 1.80wt.%. ～2.50wt.%, Zn: <0.5wt.%, Si: ≤0.15wt.%, Pb: ≤0.02wt.%, the rest are Cu, N, H, O, and the sum of the weight percentages of each component is 100%. ;

Step 3. After step 1 and step 2, pretreat the raw materials for smelting alloys and the tools used in the smelting process, and clean up the charge residue in the hearth of the intermediate frequency induction furnace;

Step 4. According to the given target value of ZCuAl8Mn13Fe3Ni2 alloy or ZCuAl8Mn14Fe3Ni2 alloy and the melting loss rate of each element in the two alloys, the batching calculation is performed respectively;

Step 5. Divide the same amount of cathode copper into four parts, take out one part and spread it on the bottom of the furnace of the intermediate frequency induction furnace; then add high-purity iron scraps, electrolytic nickel scraps, and then sprinkle crystalline silicon particles; then continue to add two parts of the cathode Copper block; finally, electrolytic manganese is added, and the charge in the furnace should be kept dense to complete the furnace loading;

Step 6. After the furnace is installed in step 5, power is supplied to raise the temperature, and the melting power is increased to melt the charge quickly. When molten metal appears in the furnace, high-purity aluminum is added in batches to promote the rapid melting of the cathode copper;

Step 7. After the melting of the charge is completed, continue to heat up, raise the temperature of the molten metal to 1300°C to 1350°C, then keep it warm for 15min to 25min, stir the molten metal to fully melt the iron filings and nickel filings; at the same time, after the molten metal is melted, pass The gas diffusion device at the bottom of the furnace feeds argon into the furnace;

Step 8. After step 7 is completed, turn off the power of the intermediate frequency induction furnace, adjust the ventilation rate, continue to ventilate, and add the remaining cathode copper and lower the temperature of the molten metal, then keep the temperature at 1050 ° C ~ 1100 ° C, and then add Industrial pure zinc and pure lead, and use graphite stirring rod for stirring;

Step 9. After step 8 is completed, raise the temperature of the molten metal to 1200°C to 1250°C, keep it warm, continue to feed argon, and use a mechanical stirring device to stir the molten metal;

Step 10, after step 9 is completed, the composition detection before the furnace is carried out;

Step 11, after step 10 is completed, carry out quality inspection of the molten metal to determine whether the molten metal is qualified;

Step 12: After step 11 judges that the quality of the molten metal is qualified, the temperature of the molten metal is controlled at 1200°C to 1230°C, after the power is turned off, the slag on the surface of the molten metal is scraped off with a slag removal tool, and a ZCuAl8Mn 13Fe3N i2 alloy or a ZCuAl8Mn14Fe3Ni2 alloy is obtained from the furnace.

The present invention is also characterized in that:

Step 1 is specifically implemented according to the following steps:

Step 1.1. Use a 250kg intermediate frequency induction furnace, and apply sealing mud three times on the furnace induction coil of the intermediate frequency induction furnace to ensure that a closed space is formed inside the furnace of the intermediate frequency induction furnace. After the sealing mud dries, add acidic lining to the intermediate frequency induction furnace material;

Step 1.2. After step 1.1, install a gas diffusion device at the center of the hearth bottom of the intermediate frequency induction furnace, and ram it from the center to the outer circumference. The acid furnace lining to be rammed is placed when the gas diffusion device is covered and the thickness reaches 40mm. For the crucible mold, keep the concentricity of the crucible mold consistent with the inductor coil, then add the acid furnace lining and continue pounding. Each layer of material should not exceed 100mm, and when adding materials, use a fork to degas first. Then pound with a flat tool;

Step 1.3. After step 1.2, add cast iron material into the hearth of the intermediate frequency induction furnace for baking. The cast iron material should be placed densely in the furnace, and the furnace should be heated slowly. The heating rate is controlled at 10°C/6min, and it is heated to 780°C Keep warm for 1 hour at ~820°C to fully remove the moisture in the acid furnace lining, then continue to heat up at a rate of 50°C/10min until the cast iron material is completely melted, then raise the furnace temperature to 1460°C-1500°C and hold for 2 hours.

Step 3 is specifically implemented as follows:

First, according to the ingredients in step 2, the raw materials for alloy preparation are respectively taken: 99.96% of cathode copper, 99.94% of high-purity aluminum, 99.95% of electrolytic manganese, 99.91% of electrolytic nickel, 99.92% of high-purity iron, 99.90% of industrial pure zinc, 99.92% of pure lead, crystal Silicon 99.97%; then clean the surface oxide of all metals to avoid foreign impurities from contaminating the metal liquid, then put the crystalline silicon and all metals into the oven for drying to remove the attached moisture and oil, during the drying process , the temperature of the oven is controlled at 210°C to 230°C; finally, the high-melting point metal Fe and metal Ni are processed into chips, and there should be no oxidation in the chips;

After step 1 is completed, clean up the furnace charge residue in the furnace of the intermediate frequency induction furnace, and if necessary, clean the furnace with cathode copper to avoid contamination of the melt by foreign matter;

The sample spoon, graphite stirring rod and slag removal tool used in the subsequent smelting process were dried separately, and the outer surfaces of the sample spoon, graphite stirring rod and slag removal tool were coated with zircon powder paint.

In step 4, the melting loss rates of each element in the two alloys are as follows:

The melting loss rate of Al is 5.0%, the melting loss rate of Mn is 2.5%, the melting loss rate of Fe is 0, the melting loss rate of Ni is 0.5%, the melting loss rate of Zn is 4.0%, and the melting loss rate of Pb is 0.5%, and the melting loss rate of Si is 0.5%.

In step 7, the argon pressure is adjusted to 0.15 MPa, and the argon flow rate is 5 L/min-15 L/min.

In step 9, the mechanical stirring speed is controlled to be 115r/min-125r/min.

Step 10 is specifically implemented as follows:

Cast the spectrum sample block in front of the furnace, process and test the end face with a lathe, calculate the amount of raw materials to be added according to the test results and the design target value, and calculate the amount of raw materials to be added.

Step 11 is specifically implemented as follows:

Get the graphite crucible and preheat the graphite crucible;

Use a sample spoon to scoop up the molten metal and pour it into the preheated graphite crucible, and place the graphite crucible containing the molten metal in a vacuum hydrogen detector. During the vacuuming stage, observe the changes on the surface of the sample as the molten metal solidifies , so as to judge the quality of molten metal, the judgment criteria are as follows:

If the center of the liquid surface of the molten metal is concave obviously, it is judged that the quality of the molten metal is qualified, and then proceed to step 12; otherwise, the quality of the molten metal is unqualified, and refining treatment must be carried out again.

The preheating temperature in step 11 is 200°C to 240°C.

The beneficial effects of the present invention are:

(1) The smelting method of the high manganese aluminum bronze alloy of the present invention can be used for the smelting process control of the high manganese aluminum bronze alloy, and can accurately control and ensure the content of each alloy element of the high manganese aluminum bronze alloy.

(2) The smelting method of the high-manganese-aluminum-bronze alloy of the present invention is reliable and easy, and the smelting is convenient, and also provides an important guarantee for energy saving and emission reduction in the alloy smelting process.

(3) The smelting method of the high-manganese-aluminum-bronze alloy of the present invention is particularly suitable for the smelting of ZCuAl8Mn13Fe3Ni2 and ZCuAl8Mn14Fe3Ni2 alloy products, which can ensure that the molten metal meets the requirements for the preparation of standard substances.

(4) The smelting method of the high-manganese-aluminum-bronze alloy of the present invention solves the problem that the content of the alloy components is difficult to be accurately controlled in the traditional process, reduces the slag inclusion and gas content in the molten metal, and effectively improves the quality of the molten metal.

detailed description

The present invention will be described in detail below in combination with specific embodiments.

The smelting method of high manganese aluminum bronze alloy of the present invention, specifically implement according to the following steps:

Step 1. First process the furnace body of the intermediate frequency induction furnace; then install a gas diffusion device at the center of the hearth bottom of the intermediate frequency induction furnace; finally add the cast iron material to the intermediate frequency induction furnace for drying, and implement according to the following steps:

Step 1.1. Use a 250kg intermediate frequency induction furnace, and apply sealing mud three times on the furnace induction coil of the intermediate frequency induction furnace to ensure that a closed space is formed inside the furnace of the intermediate frequency induction furnace. After the sealing mud dries, add acidic lining to the intermediate frequency induction furnace material;

Step 1.2. After step 1.1, install a gas diffusion device at the center of the hearth bottom of the intermediate frequency induction furnace, and ram it from the center to the outer circumference. The acid furnace lining to be rammed is placed when the gas diffusion device is covered and the thickness reaches 40mm. For the crucible mold, keep the concentricity of the crucible mold consistent with the inductor coil, then add the acid furnace lining and continue pounding. Each layer of material should not exceed 100mm, and when adding materials, use a fork to degas first. Then pound with a flat tool;

Step 1.3. After step 1.2, add cast iron material into the hearth of the intermediate frequency induction furnace for baking. The cast iron material should be placed densely in the furnace, and the furnace should be heated slowly. The heating rate is controlled at 10°C/6min, and it is heated to 780°C Keep warm for 1 hour at ~820°C to fully remove the moisture in the acid furnace lining, then continue to heat up at a rate of 50°C/10min until the cast iron material is completely melted, then raise the furnace temperature to 1460°C-1500°C and hold for 2 hours.

Step 2. After step 1 is completed, design the alloy composition according to the composition of the ZCuAl8Mn13Fe3Ni2 alloy or ZCuAl8Mn14Fe3Ni2 alloy to be smelted;

The composition of the two alloys is specifically shown in Table 1;

Table 1 Composition table of two alloys

That is, it can be seen from Table 1: 0.03

The content range of each element of ZCuAl8Mn13Fe3Ni2 alloy is:

Al: 7.00wt.%~8.50wt.%, Mn: 11.50wt.%~14.00wt.%, Fe: 2.50wt.%~4.00wt.%, Ni: 1.80wt.%~2.50wt.%, Zn: <0.5wt.%, Si: ≤0.15wt.%, Pb: ≤0.02wt.%, the rest is Cu and other impurity elements (such as: N, H, O, etc.), the sum of the weight percentage of each component is 100% ;

The content range of each element in ZCuAl8Mn14Fe3Ni2 alloy is:

Al: 7.80wt.%~8.80wt.%, Mn: 13.50wt.%~15.00wt.%, Fe: 2.80wt.%~4.00wt.%, Ni: 1.80wt.%~2.50wt.%, Zn: <0.5wt.%, Si: ≤0.15wt.%, Pb: ≤0.02wt.%, the rest is Cu and other impurity elements (such as: N, H, O, etc.), the sum of the weight percentage of each component is 100% .

Step 3. After step 1 and step 2, pretreat the raw materials for smelting alloys and the tools used in the smelting process, and clean up the residue of charge in the hearth of the intermediate frequency induction furnace. Specifically, implement according to the following methods:

According to the ingredients in step 2, the raw materials for alloy preparation are respectively taken: cathode copper (99.96%), high-purity aluminum (99.94%), electrolytic manganese (99.95%), electrolytic nickel (99.91%), high-purity iron (99.92%), industrial pure Zinc (99.90%), pure lead (99.92%), crystalline silicon (99.97%); then all metals are cleaned of surface oxides to avoid contamination of the metal liquid by foreign impurities; then the crystalline silicon and all metals are put into the oven Medium drying to remove attached moisture and oil. During the drying process, the temperature of the oven is controlled at 210°C to 230°C; finally, the high melting point metal Fe and metal Ni are processed into chips;

After step 1 is completed, clean up the furnace charge residue in the furnace of the intermediate frequency induction furnace, and if necessary, clean the furnace with cathode copper to avoid contamination of the melt by foreign matter;

The sample spoon, graphite stirring rod and slag removal tool used in the subsequent smelting process were dried separately, and the outer surfaces of the sample spoon, graphite stirring rod and slag removal tool were coated with zircon powder coating.

Step 4. According to the given target value of ZCuAl8Mn13Fe3Ni2 alloy or ZCuAl8Mn14Fe3Ni2 alloy and the melting loss rate of each element in the two alloys, the batching calculation is performed respectively;

The melting loss rate of each element in the two alloys is shown in Table 2;

Table 2 The melting loss rate table of various elements in the alloy

alloy element Al mn Fe Ni Zn Pb Si Melting loss rate/% 5.0 2.5 0 0.5 4.0 0.5 0.5

The ingredients of the two alloy standard substances are specifically shown in Table 3;

Table 3 Two kinds of alloy standard material batching list (kg)

Numbering Copper cathode High Purity Aluminum Electrolytic manganese High purity iron Electrolytic nickel pure lead pure zinc Crystalline silicon ZCuAl8Mn13Fe3Ni2 72.83 8.15 13.08 3.25 2.16 0.015 0.417 0.1 ZCuAl8Mn14Fe3Ni2 70.55 8.73 14.62 3.399 2.162 0.015 0.417 0.1

Step 5. Divide the same amount of cathode copper into four parts, take out one part and spread it on the bottom of the furnace of the intermediate frequency induction furnace; then add high-purity iron scraps, electrolytic nickel scraps, and then sprinkle crystalline silicon particles; then continue to add two parts of the cathode Copper block (remaining 1/4 cathode copper); finally add electrolytic manganese, the charge in the furnace should be kept dense, and complete the furnace loading;

Step 6. After the furnace is installed in step 5, power is supplied to raise the temperature, and the melting power is increased to melt the charge quickly. When molten metal appears in the furnace, high-purity aluminum is added in batches to promote the rapid melting of the cathode copper;

The purpose of adding high-purity aluminum in step 6 is: on the one hand, use the oxide generated by the oxidation of aluminum to adhere to the surface of the molten metal, isolate the contact between the molten metal and the air, and prevent the inhalation of gas; Thermal properties, speed up the melting of raw materials.

Step 7. After the melting of the charge is completed, continue to heat up, raise the temperature of the molten metal to 1300°C to 1350°C, then keep it warm for 15min to 25min, stir the molten metal to fully melt the iron filings and nickel filings; at the same time, after the molten metal is melted, pass The gas diffusion device at the bottom of the furnace feeds argon into the furnace;

Among them, the argon pressure is adjusted to 0.15MPa, and the flow rate is 5L/min～15L/min;

The purpose of introducing argon gas into the furnace is: the argon gas passes through the permeable bricks to form uniform small bubbles, which rise continuously. At this time, the bubbles will attach to the slag inside the molten metal, and gradually precipitate into the bubbles when they are sucked into the molten metal. In the process, as the bubbles rise, they are brought to the surface of the molten metal to remove gas and slag; the argon gas escaping from the molten metal occupies the surface of the molten metal and isolates the air to achieve the purpose of protecting the molten metal and avoiding the impact of the external environment on the surface of the molten metal. Metal liquid brings pollution.

In addition, the amount of argon gas ventilation depends on the surface conditions of the molten metal, subject to slight tumbling of the liquid surface, and there should be no splashing on the liquid surface, usually 5L/min~15L/min.

Step 8. After step 7 is completed, turn off the power of the intermediate frequency induction furnace, adjust the ventilation rate, continue to ventilate, and add the remaining cathode copper and lower the temperature of the molten metal, then keep the temperature at 1050 ° C ~ 1100 ° C, and then add Industrial pure zinc and pure lead, and use graphite stirring rod for stirring;

Step 9. After step 8 is completed (that is, after all the raw materials have been added), raise the temperature of the molten metal to 1180°C to 1250°C and keep it warm. Use a gas diffusion device to continue feeding argon into the furnace, and use a mechanical stirring device stirring molten metal;

In step 9, the purpose of stirring with a mechanical stirring device is to promote the full mixing of the alloy elements; the rate of mechanical stirring is controlled at 115r/min-125r/min.

Step 10. After step 9 is completed, the component detection before the furnace is carried out, specifically according to the following method:

Cast the spectrum sample block in front of the furnace, process and test the end face with a lathe, calculate the amount of raw materials to be added according to the test results and the design target value, and calculate the amount of raw materials to be added.

Step 11. After step 10 is completed, carry out quality inspection of the molten metal to determine whether the molten metal is qualified. Specifically, implement according to the following methods:

Take the graphite crucible and preheat the graphite crucible (the graphite crucible used for alloy liquid quality inspection must be preheated before use, and the preheating temperature is 200 ° C ~ 240 ° C);

Use a sample spoon to scoop up the molten metal and pour it into the preheated graphite crucible, and place the graphite crucible containing the molten metal in a vacuum hydrogen detector. During the vacuuming stage, observe the surface changes of the molten metal as the molten metal solidifies In order to judge the quality of molten metal, the judgment criteria are as follows:

The position of the center of the liquid surface of the molten metal is obviously concave, and it is judged that the quality of the molten metal is qualified, and then enter step 12;

Otherwise, the quality of the molten metal is unqualified, and the refining process must be carried out again.

Step 12: After step 11 judges that the quality of the molten metal is qualified, the temperature of the molten metal is controlled at 1200°C to 1230°C, after the power is turned off, the slag on the surface of the molten metal is scraped off with a slag removal tool, and a ZCuAl8Mn 13Fe3N i2 alloy or a ZCuAl8Mn14Fe3Ni2 alloy is obtained from the furnace.

Example 1

Melting of ZCuAl8Mn13Fe3Ni2 alloy:

Material preparation: Calculated by feeding 100kg, weigh 72.83kg of cathode copper, 8.15kg of high-purity aluminum, 13.08kg of electrolytic manganese, 3.25kg of high-purity iron, 2.16kg of electrolytic nickel, 0.417kg of industrial pure zinc, 0.015kg of pure lead and 0.100kg of crystalline silicon as raw material;

Clean the surface oxides of all metals to avoid foreign impurities from contaminating the molten metal; then dry the crystalline silicon and all metals in an oven to remove attached moisture and oil. During the drying process, the temperature of the oven is controlled 220°C; process high-melting-point alloy materials pure iron and pure nickel into shavings; clean up the residue of furnace materials in the furnace of the intermediate frequency induction furnace, and clean the furnace with cathode copper if necessary to avoid contamination of the melt by foreign substances; for the subsequent smelting process The used sample spoon, graphite stirring rod and slag removal tool were dried separately, and the outer surfaces of the sample spoon, graphite stirring rod and slag removal tool were coated with zircon powder paint;

Divide the cathode copper into four equal parts, take one of them and spread it on the bottom of the hearth of the intermediate frequency induction furnace; then add iron filings, electrolytic nickel filings, and then sprinkle crystalline silicon particles; then continue to add two cathode copper blocks (the remaining 1/4 cathode copper); Finally, electrolytic manganese is added, and the charge in the furnace should be kept dense to complete the furnace loading;

After the furnace is installed, power is sent to raise the temperature, and the melting power is increased to promote the rapid melting of the furnace material; when the molten metal appears in the furnace, high-purity aluminum is added in batches, and after the cathode copper is melted, continue to heat up to increase the temperature of the molten metal To 1325°C, keep warm for 20 minutes, and at the same time strengthen the stirring to promote the full melting of the charge;

After the alloy material is melted, use the gas diffusion device installed at the bottom of the furnace to introduce argon gas into the furnace. The argon gas flow rate depends on the surface conditions of the molten metal. The liquid surface is subject to slight tumbling, and there must be no splashing on the liquid surface. During the smelting process, adjust the argon pressure to 0.15MPa, and the feeding rate is 11L/min;

After the melting of the charge is completed, add the remaining cathode copper and lower the temperature of the molten metal. When the temperature of the molten metal is kept at 1070°C, add industrially pure zinc and pure lead, and stir with a graphite stirring rod;

After all the raw materials are added, raise the temperature of the molten metal to 1200°C and continue to keep warm, use the gas diffusion device to continue to introduce argon gas, and at the same time use a mechanical stirring device to stir the molten metal at a stirring rate of 120r/min, so that the alloy elements are fully mix;

Cast ZCuAl8Mn13Fe3Ni2 alloy pre-furnace spectrum sample block for component detection, and the pre-furnace detection results are shown in Table 4;

Table 4 embodiment 1ZCuAl8Mn13Fe3Ni2 alloy composition control table

Supplementary materials: 0.074kg of high-purity aluminum, 0.051kg of electrolytic manganese, 0.03kg of high-purity iron, 0.04kg of electrolytic nickel, and 0.002kg of pure lead;

Use a sample spoon to scoop high manganese aluminum bronze liquid (metal liquid) into a preheated graphite crucible, and quickly place it in a vacuum hydrogen detector, turn on the vacuum mode, and observe the solidification of high manganese aluminum bronze liquid (metal liquid) During the process, the center of the ZCuAl8Mn13Fe3Ni2 alloy sample block is deeply sunken, indicating that the quality of the melt is good;

The temperature of the molten metal is controlled at 1210°C, the power is turned off, and the slag on the surface of the molten alloy is scraped off with a slag removal tool, and the ZCuAl8Mn13Fe3Ni2 alloy is obtained after being discharged from the furnace.

Example 2

Melting of ZCuAl8Mn13Fe3Ni2 alloy:

Material preparation: Calculated by feeding 100kg, weigh 72.83kg of cathode copper, 8.15kg of high-purity aluminum, 13.08kg of electrolytic manganese, 3.25kg of high-purity iron, 2.16kg of electrolytic nickel, 0.417kg of industrial pure zinc, 0.015kg of pure lead and 0.100kg of crystalline silicon as raw material;

Clean the surface oxides of all metals to avoid foreign impurities from contaminating the molten metal; then dry the crystalline silicon and all metals in an oven to remove attached moisture and oil. During the drying process, the temperature of the oven is controlled 230°C; process high-melting-point metal Fe and metal Ni into shavings; clean up the furnace material residue in the furnace of the intermediate frequency induction furnace, and clean the furnace with cathode copper if necessary to avoid contamination of the melt by foreign matter; for the subsequent smelting process The sample spoon, graphite stirring rod and slag removal tool were dried separately, and the outer surfaces of the sample spoon, graphite stirring rod and slag removal tool were coated with zircon powder paint;

Divide the cathode copper into four equal parts, spread one of them on the bottom of the hearth of the intermediate frequency induction furnace; then add iron scraps, electrolytic nickel scraps, and sprinkle crystalline silicon particles; then continue to add two cathode copper blocks (the remaining 1/4 cathode copper); Finally, electrolytic manganese is added, and the charge in the furnace should be kept dense to complete the furnace loading;

After the furnace is installed, power is sent to raise the temperature, and the melting power is increased to promote the rapid melting of the furnace material; when the molten metal appears in the furnace, high-purity aluminum is added in batches, and after the cathode copper is melted, continue to heat up to increase the temperature of the molten metal To 1350°C, keep warm for 15 minutes, and at the same time strengthen the stirring to promote the full melting of the charge;

When there is a liquid surface in the furnace body of the intermediate frequency induction furnace, use the gas diffusion device installed at the bottom of the furnace to introduce argon into the furnace body. The amount of argon gas ventilation depends on the surface of the molten metal. There should be no splash on the liquid surface, adjust the argon pressure to 0.15MPa, and the flow rate is 15L/min;

After the melting of the charge is completed, add the remaining cathode copper, lower the temperature of the molten metal, and keep the temperature at 1100°C, add industrial pure zinc and pure lead, and stir with a graphite stirring rod;

After all the raw materials are added, the temperature of the molten metal is raised to 1250°C and kept warm, and the gas diffusion device is used to continue to introduce argon gas.

At the same time, a mechanical stirring device is used to stir the molten metal, and the stirring rate is 125r/min, so as to promote the full mixing of all alloy elements;

Cast the ZCuAl8Mn13Fe3Ni2 alloy pre-furnace spectrum sample block for composition detection, and the pre-furnace detection results are shown in Table 4 above;

Supplementary materials: 0.074kg of high-purity aluminum, 0.051kg of electrolytic manganese, 0.03kg of high-purity iron, 0.04kg of electrolytic nickel, and 0.002kg of pure lead;

Use a sample spoon to scoop high manganese aluminum bronze liquid (metal liquid) into a preheated graphite crucible, and quickly place it in a vacuum hydrogen detector, turn on the vacuum mode, and observe the solidification of high manganese aluminum bronze liquid (metal liquid) During the process, the center of the ZCuAl8Mn13Fe3Ni2 alloy sample block is deeply sunken, indicating that the quality of the melt is good;

The temperature of the molten metal is controlled at 1230°C, the power is turned off, and the slag on the surface of the molten alloy is scraped off with a slag removal tool, and the ZCuAl8Mn13Fe3Ni2 alloy is obtained after being discharged from the furnace.

Example 3

Melting of ZCuAl8Mn14Fe3Ni2 alloy:

Material preparation: Calculated by feeding 100kg, weigh 70.55kg of cathode copper, 8.73kg of high-purity aluminum, 14.62kg of electrolytic manganese, 3.399kg of high-purity iron, 2.162kg of electrolytic nickel, 0.417kg of industrial pure zinc, 0.015kg of pure lead and 0.100kg of crystalline silicon as raw material;

Clean the surface oxides of all metals to avoid foreign impurities from contaminating the molten metal; then dry the crystalline silicon and all metals in an oven to remove attached moisture and oil. During the drying process, the temperature of the oven is controlled 210°C; process high melting point metal Fe and metal Ni into shavings; clean up the furnace material residue in the intermediate frequency induction furnace, and if necessary, use cathode copper to clean the furnace to avoid contamination of the melt by foreign matter; for subsequent smelting process The sample spoon, graphite stirring rod and slag removal tool were dried separately, and the outer surfaces of the sample spoon, graphite stirring rod and slag removal tool were coated with zircon powder paint;

Divide the cathode copper into four equal parts, one of which is placed on the bottom of the furnace of the intermediate frequency induction furnace; then add iron filings, electrolytic nickel filings, and then sprinkle crystalline silicon particles; then continue to add two cathode copper blocks (remaining 1/ 4 cathode copper); Finally, electrolytic manganese is added, and the charge in the furnace should be kept compact to complete the furnace loading;

After the furnace is installed, power is sent to raise the temperature, and the melting power is increased to promote the rapid melting of the furnace material; when the molten metal appears in the furnace, high-purity aluminum is added in batches, and after the cathode copper is melted, continue to heat up to increase the temperature of the molten metal To 1300 ℃, keep warm for 25 minutes, and at the same time strengthen the stirring to promote the full melting of the charge;

When there is a liquid surface in the furnace body of the intermediate frequency induction furnace, use the gas diffusion device installed at the bottom of the furnace to introduce argon into the furnace body. The amount of argon gas ventilation depends on the surface of the molten metal. There should be no splashing on the liquid surface. During the smelting process, adjust the argon pressure to 0.15MPa, and the flow rate is 5L/min;

After the melting of the charge is completed, add the remaining cathode copper, lower the temperature of the molten metal, keep the temperature at 1050°C, add industrial pure zinc and pure lead, and stir with a graphite stirring rod;

After all the raw materials are added, raise the temperature of the molten metal to 1180°C and keep it warm, use the gas diffusion device to continue to feed argon gas, and at the same time use a mechanical stirring device to stir the molten metal at a stirring rate of 115r/min to promote the full mixing of the alloy elements ;

Casting ZCuAl8Mn14Fe3Ni2 alloy furnace front spectrum sample block for composition detection;

Use a sample spoon to scoop the high-manganese-aluminum bronze liquid into the preheated graphite crucible, and quickly place it in the vacuum hydrogen detector, turn on the vacuum mode, and observe the solidification process of the molten metal. The center of the ZCuAl8Mn14Fe3Ni2 alloy sample block is deep, Indicates that the quality of the melt is good;

The temperature of the molten metal is controlled at 1200°C, the power is turned off, and the slag on the surface of the alloy liquid is scraped off with a slag removal tool, and the ZCuAl8Mn14Fe3Ni2 alloy is obtained after being discharged from the furnace.

The method for smelting high-manganese-aluminum-bronze alloys of the present invention is specifically a method for smelting copper alloys using an intermediate frequency induction furnace in an atmospheric environment, and is mainly used for smelting ZCuAl8Mn13Fe3Ni2 alloys or ZCuAl8Mn14Fe3Ni2 alloys to ensure that the molten metal meets the requirements for the preparation of standard substances, and solves the problem of The problem that the content of the alloy composition cannot be precisely controlled under the traditional process, while reducing the slag inclusion and gas content in the molten metal, improves the quality of the molten metal. In a word, the smelting method of high manganese aluminum bronze alloy of the present invention is mainly used in the smelting process of preparing high manganese aluminum bronze standard material ingots, and can also be used in the production process of products with higher requirements on the quality of such alloy castings.

Claims (9)

1. the smelting method of high manganese aluminum bronze alloy is characterized in that, specifically implement according to the following steps: Step 1. First process the furnace body of the intermediate frequency induction furnace; then install a gas diffusion device at the center of the hearth bottom of the intermediate frequency induction furnace; finally add the cast iron material to the intermediate frequency induction furnace for baking; Step 2. After step 1 is completed, design the alloy composition according to the composition of the ZCuAl8Mn13Fe3Ni2 alloy or ZCuAl8Mn14Fe3Ni2 alloy to be smelted; The content range of ZCuAl8Mn13Fe3Ni2 alloy elements is: Al: 7.00wt.% ~ 8.50wt.%, Mn: 11.50wt.% ~ 14.00wt.%, Fe: 2.50wt.% ~ 4.00wt.%, Ni: 1.80wt.%. ～2.50wt.%, Zn: <0.5wt.%, Si: ≤0.15wt.%, Pb: ≤0.02wt.%, the rest are Cu, N, H, O, and the sum of the weight percentages of each component is 100%. ; The content range of ZCuAl8Mn14Fe3Ni2 alloy elements is: Al: 7.80wt.% ~ 8.80wt.%, Mn: 13.50wt.% ~ 15.00wt.%, Fe: 2.80wt.% ~ 4.00wt.%, Ni: 1.80wt.%. ～2.50wt.%, Zn: <0.5wt.%, Si: ≤0.15wt.%, Pb: ≤0.02wt.%, the rest are Cu, N, H, O, and the sum of the weight percentages of each component is 100%. ; Step 3. After step 1 and step 2, pretreat the raw materials for smelting alloys and the tools used in the smelting process, and clean up the charge residue in the hearth of the intermediate frequency induction furnace; Step 4. According to the given target value of ZCuAl8Mn13Fe3Ni2 alloy or ZCuAl8Mn14Fe3Ni2 alloy and the melting loss rate of each element in the two alloys, the batching calculation is performed respectively; Step 5. Divide the same amount of cathode copper into four parts, take out one part and spread it on the bottom of the furnace of the intermediate frequency induction furnace; then add high-purity iron scraps, electrolytic nickel scraps, and then sprinkle crystalline silicon particles; then continue to add two parts of the cathode Copper block; finally, electrolytic manganese is added, and the charge in the furnace should be kept dense to complete the furnace loading; Step 6. After the furnace is installed in step 5, power is supplied to raise the temperature, and the melting power is increased to melt the charge quickly. When molten metal appears in the furnace, high-purity aluminum is added in batches to promote the rapid melting of the cathode copper; Step 7. After the melting of the charge is completed, continue to heat up, raise the temperature of the molten metal to 1300°C to 1350°C, then keep it warm for 15min to 25min, stir the molten metal to fully melt the iron filings and nickel filings; at the same time, after the molten metal is melted, pass The gas diffusion device at the bottom of the furnace feeds argon into the furnace; Step 8. After step 7 is completed, turn off the power of the intermediate frequency induction furnace, adjust the ventilation rate, continue to ventilate, and add the remaining cathode copper and lower the temperature of the molten metal, then keep the temperature at 1050 ° C ~ 1100 ° C, and then add Industrial pure zinc and pure lead, and use graphite stirring rod for stirring; Step 9. After step 8 is completed, raise the temperature of the molten metal to 1200°C to 1250°C, keep it warm, continue to feed argon, and use a mechanical stirring device to stir the molten metal; Step 10, after step 9 is completed, the composition detection before the furnace is carried out; Step 11, after step 10 is completed, carry out quality inspection of the molten metal to determine whether the molten metal is qualified; Step 12: After step 11 judges that the quality of the molten metal is qualified, the temperature of the molten metal is controlled at 1200°C to 1230°C, after the power is turned off, the slag on the surface of the molten metal is scraped off with a slag removal tool, and a ZCuAl8Mn 13Fe3N i2 alloy or a ZCuAl8Mn14Fe3Ni2 alloy is obtained from the furnace. 2. the smelting method of high manganese aluminum bronze alloy according to claim 1, is characterized in that, described step 1 is specifically implemented according to the following steps: Step 1.1. Use a 250kg intermediate frequency induction furnace, and apply sealing mud three times on the furnace induction coil of the intermediate frequency induction furnace to ensure that a closed space is formed inside the furnace of the intermediate frequency induction furnace. After the sealing mud dries, add acidic lining to the intermediate frequency induction furnace material; Step 1.2. After step 1.1, install a gas diffusion device at the center of the hearth bottom of the intermediate frequency induction furnace, and ram it from the center to the outer circumference. The acid furnace lining to be rammed is placed when the gas diffusion device is covered and the thickness reaches 40mm. For the crucible mold, keep the concentricity of the crucible mold consistent with the inductor coil, then add the acid furnace lining and continue pounding. Each layer of material should not exceed 100mm, and when adding materials, use a fork to degas first. Then pound with a flat tool; Step 1.3. After step 1.2, add cast iron material into the hearth of the intermediate frequency induction furnace for baking. The cast iron material should be placed densely in the furnace, and the furnace should be heated slowly. The heating rate is controlled at 10°C/6min, and it is heated to 780°C Keep warm for 1 hour at ~820°C to fully remove the moisture in the acid furnace lining, then continue to heat up at a rate of 50°C/10min until the cast iron material is completely melted, then raise the furnace temperature to 1460°C-1500°C and hold for 2 hours. 3. the smelting method of high manganese aluminum bronze alloy according to claim 1, is characterized in that, described step 3 is specifically implemented according to the following method: First, according to the ingredients in step 2, the raw materials for alloy preparation are respectively taken: 99.96% of cathode copper, 99.94% of high-purity aluminum, 99.95% of electrolytic manganese, 99.91% of electrolytic nickel, 99.92% of high-purity iron, 99.90% of industrial pure zinc, 99.92% of pure lead, crystal Silicon 99.97%; then clean the surface oxide of all metals to avoid foreign impurities from contaminating the metal liquid, then put the crystalline silicon and all metals into the oven for drying to remove the attached moisture and oil, during the drying process , the temperature of the oven is controlled at 210°C to 230°C; finally, the high-melting point metal Fe and metal Ni are processed into chips, and there should be no oxidation in the chips; After step 1 is completed, clean up the furnace charge residue in the furnace of the intermediate frequency induction furnace, and if necessary, clean the furnace with cathode copper to avoid contamination of the melt by foreign matter; The sample spoon, graphite stirring rod and slag removal tool used in the subsequent smelting process were dried separately, and the outer surfaces of the sample spoon, graphite stirring rod and slag removal tool were coated with zircon powder coating. 4. the smelting method of high manganese aluminum bronze alloy according to claim 1 is characterized in that, in described step 4, the melting rate of each element in two kinds of alloys is respectively as follows: The melting loss rate of Al is 5.0%, the melting loss rate of Mn is 2.5%, the melting loss rate of Fe is 0, the melting loss rate of Ni is 0.5%, the melting loss rate of Zn is 4.0%, and the melting loss rate of Pb is 0.5%, and the melting loss rate of Si is 0.5%. 5. The method for smelting high-manganese-aluminum-bronze alloys according to claim 1, characterized in that, in the step 7, the argon pressure is adjusted to 0.15MPa, and the argon flow rate is 5L/min-15L /min. 6 . The method for smelting high manganese aluminum bronze alloy according to claim 1 , characterized in that, in the step 9, the mechanical stirring rate is controlled to be 115r/min˜125r/min. 7. the smelting method of high manganese aluminum bronze alloy according to claim 1, is characterized in that, described step 10 is specifically implemented according to the following method: Cast the spectrum sample block in front of the furnace, process and test the end face with a lathe, calculate the amount of raw materials to be added according to the test results and the design target value, and calculate the amount of raw materials to be added. 8. the smelting method of high manganese aluminum bronze alloy according to claim 1, is characterized in that, described step 11 is specifically implemented according to the following method: Get the graphite crucible and preheat the graphite crucible; Use a sample spoon to scoop up the molten metal and pour it into the preheated graphite crucible, and place the graphite crucible containing the molten metal in a vacuum hydrogen detector. During the vacuuming stage, observe the changes on the surface of the sample as the molten metal solidifies , so as to judge the quality of molten metal, the judgment criteria are as follows: If the center of the liquid surface of the molten metal is concave obviously, it is judged that the quality of the molten metal is qualified, and then proceed to step 12; otherwise, the quality of the molten metal is unqualified, and refining treatment must be carried out again. 9. The method for smelting high manganese aluminum bronze alloy according to claim 8, characterized in that, the preheating temperature in the step 11 is 200°C-240°C.