CN113215437A - Copper material for valve and preparation method of valve - Google Patents

Copper material for valve and preparation method of valve Download PDF

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Publication number
CN113215437A
CN113215437A CN202110487042.2A CN202110487042A CN113215437A CN 113215437 A CN113215437 A CN 113215437A CN 202110487042 A CN202110487042 A CN 202110487042A CN 113215437 A CN113215437 A CN 113215437A
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China
Prior art keywords
valve
copper
copper material
mold
copper alloy
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Pending
Application number
CN202110487042.2A
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Chinese (zh)
Inventor
王朝阳
祝云霞
杨月红
胡朝辉
王帅
王晓晓
王玉堂
戴春光
杨骑峰
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Ningbo Huacheng Valve Co ltd
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Ningbo Huacheng Valve Co ltd
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Priority to CN202110487042.2A priority Critical patent/CN113215437A/en
Publication of CN113215437A publication Critical patent/CN113215437A/en
Pending legal-status Critical Current

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/22—Moulds for peculiarly-shaped castings
    • B22C9/24—Moulds for peculiarly-shaped castings for hollow articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
    • B22D27/04—Influencing the temperature of the metal, e.g. by heating or cooling the mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
    • B22D27/20—Measures not previously mentioned for influencing the grain structure or texture; Selection of compositions therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D31/00—Cutting-off surplus material, e.g. gates; Cleaning and working on castings
    • B22D31/002—Cleaning, working on castings
    • 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
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/02—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Powder Metallurgy (AREA)
  • Conductive Materials (AREA)

Abstract

The invention belongs to the technical field of alloy, and particularly relates to a copper material for a valve and a preparation method of the valve. The copper material for the valve comprises the following raw materials in percentage by mass: RE 0.5-1.0%, Mo 0.6-1.5%, V0.5-1%, Ni 1-5%, Ti 0.3-1%, Al 2-5%, and the balance of copper and inevitable impurities. The copper material for the valve and the valve made of the copper material have the advantages of antibiosis, abrasion resistance, corrosion resistance, good cutting performance, high safety, shock and heat resistance, good cold and hot processing performance and suitability for various application environments.

Description

Copper material for valve and preparation method of valve
Technical Field
The invention belongs to the technical field of alloy, and particularly relates to a copper material for a valve and a preparation method of the valve.
Background
The valve is a control part in a pipeline fluid conveying system, is used for changing the section of a passage and the flowing direction of a medium, and has the functions of diversion, cut-off, throttling, non-return, flow splitting, overflow pressure relief and the like. The copper alloy valve is one of valves and plays a key role in many fields, but because the application fields of the copper valves are different, higher requirements are provided for the performance of the current valve, such as antibiosis, corrosion resistance, shock resistance and chilling and heating resistance, and the cold and hot processing performance is better, so that the copper alloy valve can be applied to various application environments.
Disclosure of Invention
Aiming at the problems, the invention provides a copper material for a valve and a preparation method of the valve.
The invention relates to a copper material for a valve, which comprises the following raw materials in percentage by mass: RE 0.5-1.0%, Mo 0.6-1.5%, V0.5-1%, Ni 1-5%, Ti 3-10%, Al 0.2-0.5%, and the balance of copper and inevitable impurities.
Preferably, the copper material comprises the following raw materials in percentage by mass: RE0.8%, Mo1.0%, V0.5%, Ni 2%, Ti 0.5%, Al 3%, and the balance of copper and unavoidable impurities.
And RE is mixed rare earth with cerium content not less than 50% in percentage by mass.
The invention also provides a preparation method of the valve, which adopts the copper material for the valve and comprises the following specific steps:
(1) weighing the raw materials in proportion for later use;
(2) smelting: adding 40-45% of pure copper ingots, heating to 1200-1300 ℃ after the pure copper ingots are melted, then sequentially adding Mo, V, Ni, Ti, Al and RE, uniformly stirring, and keeping the temperature for 10-15 min; adding the rest of pure copper ingot, uniformly stirring, heating to 1300-1350 ℃, and smelting for 15-20 min to obtain a smelted mixed solution;
(3) pouring: pouring the mixed solution obtained in the step (2) into a valve mold, cooling the in-mold casting to 1000 +/-10 ℃, opening the mold, taking out the formed blank, cooling to 300-200 ℃ within 4-6 min, and then air-cooling to room temperature to obtain a copper alloy valve rough blank;
(4) spraying: and (3) treating the surface of the copper alloy valve rough blank, immersing the treated surface in passivation preservative solution for 10-20min, taking out, curing and drying to obtain the copper alloy valve.
In the step (3), tellurium powder is brushed in the valve die; the tellurium powder accounts for 5-7 wt% of the basic raw material.
In the step (4), the preparation process of the passivation and corrosion-resistant solution comprises the following steps: under the protection of N2, dissolving benzotriazole and maleic acid in methanol, stirring for 2-3h at 20-50 ℃ to obtain passivation anticorrosive solution.
In terms of molar ratio, benzotriazole: maleic acid =2-3: 1.
In the invention, the rare earth is added, so that the copper material has a certain antibacterial effect, and the strength of the aluminum alloy is easily improved. When the RE content is less than 0.5%, the rare earth cannot achieve the antibacterial effect. But the content of rare earth elements is too high, which not only increases the cost, but also reduces the plasticity and the forming performance of copper materials. The rare earth content of the invention is preferably 0.5-1.0%. In addition, the rare earth elements enable compact crystal grains to be formed in the copper material, the crystal grains are uniformly distributed, the strength of the copper material is improved, the comprehensive performance of the copper material is improved, and unexpected technical effects are generated. The addition of Mo element can raise corrosion resistance and strength, the addition of W element can raise hardness and wear resistance of copper material, and the addition of V element can refine crystal grains in heat treatment and raise strength and toughnessAnd the Ni is added, so that the wear resistance and the strength of the alloy can be improved, the melting point of the alloy can be improved, and the high-temperature resistance of the alloy can be improved. The present invention contains Ti, and Ti forms Al with aluminum3Ti phase, and improves the strength and plasticity of the copper material. The Ti and the RE can reduce the damage to the plasticity and the forming performance of the alloy, so the Ti content is controlled to be 0.3-1.0 percent.
Tellurium is used as the main alloy element and has the purpose of improving the cutting performance, because the metal Te exists in the crystal boundary or the crystal as a simple substance and forms Cu2Te metal compound, thereby improving the cutting rate in the cutting process, namely improving the machinability without causing the reduction of the conductivity of the material; the invention coats tellurium powder in the valve mould, then pours the smelted mixed liquid into the mould, avoids the burning loss of tellurium to a certain extent, and when tellurium is added into the molten metal, it can stimulate violent reaction, and impels the metal liquid to deoxidize in a short time, and makes the metal liquid cool rapidly, the solidification speed is accelerated greatly, thus preventing the compact casting, and further improving the high temperature resistance, impact resistance, wear resistance, chilling and heat resistance of the product.
The benzotriazole used in the invention has different numbers of nitrogen atom adsorption sites and different presented spatial structures, can effectively isolate corrosive media, and is beneficial to forming a protective film on the metal surface. The maleic acid contains carboxyl or unsaturated bonds, which is beneficial to the adsorption on the metal surface. The two are used together, the synergistic effect between the two is enhanced, the charge density around the cation or anion is higher, the adsorption capacity of the passivation preservative solution on the metal surface is enhanced, the repulsive force to an acidic aqueous solution is stronger, the preservative performance can be obviously improved, and further, the good preservative effect is shown in a strong acidic environment. The test shows that the corrosion rate of the valve is reduced by 7.62 percent compared with the corrosion rate of the conventional copper valve.
The copper material for the valve and the valve made of the copper material have the advantages of antibiosis, abrasion resistance, corrosion resistance, good cutting performance, high safety, shock and heat resistance, good cold and hot processing performance and suitability for various application environments.
Detailed Description
Example 1
A copper material for a valve comprises the following raw materials in percentage by mass: 0.5% of RE, 1.5% of Mo, 0.5% of V, 3% of Ni, 0.5% of Ti, 3% of Al, and the balance of copper and inevitable impurities.
And RE is mixed rare earth with cerium content not less than 50% in percentage by mass.
The preparation method of the valve adopts the copper material for the valve, and comprises the following specific steps:
(1) weighing the raw materials in proportion for later use;
(2) smelting: adding 40% of pure copper ingot, heating to 1200 ℃ after the pure copper ingot is melted, then sequentially adding Mo, V, Ni, Ti, Al and RE, stirring uniformly, and keeping the temperature for 15 min; adding the rest of pure copper ingot, uniformly stirring, heating to 1300 ℃, and smelting for 15min to obtain a smelted mixed solution;
(3) pouring: pouring the mixed solution obtained in the step (2) into a valve mold, cooling the in-mold casting to 1000 +/-10 ℃, opening the mold, taking out the formed blank, cooling to 200 ℃ within 4-6 min, and then cooling to room temperature in air to obtain the copper alloy valve.
(4) Spraying: and (3) treating the surface of the copper alloy valve rough blank, immersing the treated surface in passivation preservative solution for 20min, taking out, curing and drying to obtain the copper alloy valve.
In the step (3), tellurium powder is brushed in the valve die; the using amount of the tellurium powder is 5wt% of that of the basic raw material.
In the step (4), the preparation process of the passivation and corrosion-resistant solution comprises the following steps: under the protection of N2, benzotriazole and maleic acid are dissolved in methanol, stirred at 20 ℃ for 2h to obtain passivation preservative solution.
In terms of molar ratio, benzotriazole: maleic acid =2: 1.
Example 2
A copper material for a valve comprises the following raw materials in percentage by mass: RE 0.6%, Mo 0.6%, V1%, Ni 1%, Ti 1%, Al 5%, and the balance of copper and unavoidable impurities.
And RE is mixed rare earth with cerium content not less than 50% in percentage by mass.
The preparation method of the valve adopts the copper material for the valve, and comprises the following specific steps:
(1) weighing the raw materials in proportion for later use;
(2) smelting: firstly adding 45% of pure copper ingot, heating to 1300 ℃ after the pure copper ingot is melted, then sequentially adding Mo, V, Ni, Ti, Al and RE, uniformly stirring, and keeping the temperature for 10 min; adding the rest of pure copper ingot, uniformly stirring, heating to 1350 ℃, and smelting for 20min to obtain a smelted mixed solution;
(3) pouring: pouring the mixed solution obtained in the step (2) into a valve mold, cooling the in-mold casting to 1000 +/-10 ℃, opening the mold, taking out the formed blank, cooling to 300 ℃ within 4-6 min, and then cooling to room temperature in air to obtain the copper alloy valve.
(4) Spraying: and (3) treating the surface of the copper alloy valve rough blank, immersing the treated surface in passivation preservative solution for 10min, taking out, curing and drying to obtain the copper alloy valve.
In the step (3), tellurium powder is brushed in the valve die; the using amount of the tellurium powder is 7wt% of that of the basic raw material.
In the step (4), the preparation process of the passivation and corrosion-resistant solution comprises the following steps: under the protection of N2, benzotriazole and maleic acid are dissolved in methanol, stirred at 50 ℃ for 2h to obtain passivation preservative solution.
In terms of molar ratio, benzotriazole: maleic acid =3: 1.
Example 3
A copper material for a valve comprises the following raw materials in percentage by mass: RE0.8%, Mo1.0%, V0.6%, Ni 5%, Ti 0.3%, Al 2%, and the balance of copper and unavoidable impurities.
And RE is mixed rare earth with cerium content not less than 50% in percentage by mass.
The preparation method of the valve adopts the copper material for the valve, and comprises the following specific steps:
(1) weighing the raw materials in proportion for later use;
(2) smelting: firstly adding 45% of pure copper ingot, heating to 1200 ℃ after the pure copper ingot is melted, then sequentially adding Mo, V, Ni, Ti, Al and RE, uniformly stirring, and keeping the temperature for 10 min; adding the rest of pure copper ingot, uniformly stirring, heating to 1300 ℃, and smelting for 20min to obtain a smelted mixed solution;
(3) pouring: pouring the mixed solution obtained in the step (2) into a valve mold, cooling the in-mold casting to 1000 +/-10 ℃, opening the mold, taking out the formed blank, cooling to 300 ℃ within 4-6 min, and then cooling to room temperature in air to obtain the copper alloy valve.
(4) Spraying: and (3) treating the surface of the copper alloy valve rough blank, immersing the treated surface in passivation preservative solution for 10min, taking out, curing and drying to obtain the copper alloy valve.
In the step (3), tellurium powder is brushed in the valve die; the using amount of the tellurium powder is 6wt% of that of the basic raw material.
In the step (4), the preparation process of the passivation and corrosion-resistant solution comprises the following steps: under the protection of N2, benzotriazole and maleic acid are dissolved in methanol, stirred for 3 hours at 2300 ℃ to obtain passivation preservative solution.
In terms of molar ratio, benzotriazole: maleic acid =3: 1.
Example 4
A copper material for a valve comprises the following raw materials in percentage by mass: RE 1.0%, Mo 0.8%, V0.8%, Ni 3%, Ti 0.6%, Al 2%, and the balance copper and inevitable impurities.
And RE is mixed rare earth with cerium content not less than 50% in percentage by mass.
The preparation method of the valve adopts the copper material for the valve, and comprises the following specific steps:
(1) weighing the raw materials in proportion for later use;
(2) smelting: adding 40% of pure copper ingot, heating to 1300 ℃ after the pure copper ingot is melted, then sequentially adding Mo, V, Ni, Ti, Al and RE, stirring uniformly, and keeping the temperature for 15 min; adding the rest of pure copper ingot, uniformly stirring, heating to 1350 ℃, and smelting for 15min to obtain a smelted mixed solution;
(3) pouring: pouring the mixed solution obtained in the step (2) into a valve mold, cooling the in-mold casting to 1000 +/-10 ℃, opening the mold, taking out the formed blank, cooling to 300 ℃ within 4-6 min, and then cooling to room temperature in air to obtain the copper alloy valve.
(4) Spraying: and (3) treating the surface of the copper alloy valve rough blank, immersing the treated surface in passivation preservative solution for 10min, taking out, curing and drying to obtain the copper alloy valve.
In the step (3), tellurium powder is brushed in the valve die; the using amount of the tellurium powder is 7wt% of that of the basic raw material.
In the step (4), the preparation process of the passivation and corrosion-resistant solution comprises the following steps: under the protection of N2, benzotriazole and maleic acid are dissolved in methanol, stirred at 40 ℃ for 2h to obtain passivation preservative solution.
In terms of molar ratio, benzotriazole: maleic acid =2.5: 1.
Example 5
A copper material for a valve comprises the following raw materials in percentage by mass: RE0.8%, Mo1.0%, V0.5%, Ni 2%, Ti 0.5%, Al 3%, and the balance of copper and unavoidable impurities.
And RE is mixed rare earth with cerium content not less than 50% in percentage by mass.
The preparation method of the valve adopts the copper material for the valve, and comprises the following specific steps:
(1) weighing the raw materials in proportion for later use;
(2) smelting: firstly adding 45% of pure copper ingot, heating to 1300 ℃ after the pure copper ingot is melted, then sequentially adding Mo, V, Ni, Ti, Al and RE, uniformly stirring, and keeping the temperature for 15 min; adding the rest of pure copper ingot, uniformly stirring, heating to 1350 ℃, and smelting for 15min to obtain a smelted mixed solution;
(3) pouring: pouring the mixed solution obtained in the step (2) into a valve mold, cooling the in-mold casting to 1000 +/-10 ℃, opening the mold, taking out the formed blank, cooling to 200 ℃ within 4-6 min, and then cooling to room temperature in air to obtain the copper alloy valve.
(4) Spraying: and (3) treating the surface of the copper alloy valve rough blank, immersing the treated surface in passivation preservative solution for 10min, taking out, curing and drying to obtain the copper alloy valve.
In the step (3), tellurium powder is brushed in the valve die; the using amount of the tellurium powder is 6wt% of that of the basic raw material.
In the step (4), the preparation process of the passivation and corrosion-resistant solution comprises the following steps: in N2Under protection, benzotriazole and maleic acid are dissolved in methanol, stirred at 50 ℃ for 3h to obtain passivation preservative solution.
In terms of molar ratio, benzotriazole: maleic acid =2: 1.
TABLE 1 copper alloy property test results obtained by the present invention
Numbering Tensile strength/MPa Wear rate mg/Km Machinability and cutting property anti-E.coli ratio/%)
Example 1 760 50 90% 99.9
Example 2 740 53 90% 99.9
Example 3 780 58 90% 99.9
Example 4 750 56 90% 99.9
Example 5 800 57 90% 99.9

Claims (7)

1. The copper material for the valve is characterized by comprising the following raw materials in percentage by mass: RE 0.5-1.0%, Mo 0.6-1.5%, V0.5-1%, Ni 1-5%, Ti 0.3-1%, Al 2-5%, and the balance of copper and inevitable impurities.
2. The copper alloy for the valve according to claim 1, wherein the copper material comprises the following raw materials in percentage by mass: RE0.8%, Mo1.0%, V0.5%, Ni 2%, Ti 0.5%, Al 3%, and the balance of copper and unavoidable impurities.
3. The valve copper alloy according to claim 1, wherein the RE is a misch metal having a cerium content of not less than 50% by mass.
4. A method for preparing a valve, which is characterized in that the copper material for the valve according to any one of claims 1 to 3 is adopted, and the method comprises the following specific steps:
(1) weighing the raw materials in proportion for later use;
(2) smelting: adding 40-45% of pure copper ingots, heating to 1200-1300 ℃ after the pure copper ingots are melted, then sequentially adding Mo, V, Ni, Ti, Al and RE, uniformly stirring, and keeping the temperature for 10-15 min; adding the rest of pure copper ingot, uniformly stirring, heating to 1300-1350 ℃, and smelting for 15-20 min to obtain a smelted mixed solution;
(3) pouring: pouring the mixed solution obtained in the step (2) into a valve mold, cooling the in-mold casting to 1000 +/-10 ℃, opening the mold, taking out the formed blank, cooling to 300-200 ℃ within 4-6 min, and then air-cooling to room temperature to obtain a copper alloy valve rough blank;
(4) spraying: and (3) treating the surface of the copper alloy valve rough blank, immersing the treated surface in passivation preservative solution for 10-20min, taking out, curing and drying to obtain the copper alloy valve.
5. The method for preparing the valve according to claim 4, wherein in the step (3), tellurium powder is coated in the valve mold; the tellurium powder accounts for 5-7 wt% of the basic raw material.
6. The method for preparing the valve according to claim 4, wherein in the step (4), the passivation preservative solution is prepared by the following steps: under the protection of N2, dissolving benzotriazole and maleic acid in methanol, stirring for 2-3h at 20-50 ℃ to obtain passivation anticorrosive solution.
7. The method for preparing the valve according to claim 4, wherein the molar ratio of benzotriazole: maleic acid =2-3: 1.
CN202110487042.2A 2021-05-04 2021-05-04 Copper material for valve and preparation method of valve Pending CN113215437A (en)

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