CN113718130B - As-cast high-strength manganese-aluminum bronze alloy and preparation method thereof - Google Patents
As-cast high-strength manganese-aluminum bronze alloy and preparation method thereof Download PDFInfo
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- CN113718130B CN113718130B CN202010453646.0A CN202010453646A CN113718130B CN 113718130 B CN113718130 B CN 113718130B CN 202010453646 A CN202010453646 A CN 202010453646A CN 113718130 B CN113718130 B CN 113718130B
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- 229910000906 Bronze Inorganic materials 0.000 title claims abstract description 29
- -1 manganese-aluminum Chemical compound 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 30
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 238000007670 refining Methods 0.000 claims description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 22
- 229910052802 copper Inorganic materials 0.000 claims description 22
- 238000005266 casting Methods 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- 239000011572 manganese Substances 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 239000010974 bronze Substances 0.000 claims description 12
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 10
- 239000000956 alloy Substances 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 8
- 239000010962 carbon steel Substances 0.000 claims description 8
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 239000011888 foil Substances 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 abstract description 12
- 229910052759 nickel Inorganic materials 0.000 abstract description 8
- 229910052742 iron Inorganic materials 0.000 abstract description 4
- 229910000881 Cu alloy Inorganic materials 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000003610 charcoal Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000006392 deoxygenation reaction Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009750 centrifugal casting Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- C22C9/05—Alloys based on copper with manganese as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to an as-cast high-strength manganese-aluminum bronze alloy and a preparation method thereof, belonging to the technical field of copper alloys. The cast high-strength manganese-aluminum bronze alloy comprises the following components in percentage by mass: 12.5-13.5% Mn, 7.8-8.3% Al, 1.9-2.2% Ni, 3.1-3.3% Fe, 0.1-0.15% Be, 0.01% or less of Zn, 0.01% or less of C, the mass ratio of Al to Mn being 1:1.5 to 1.65, and the balance of Cu. The high-strength manganese-aluminum bronze alloy strictly controls the content of each element of Mn, al, ni, fe and Be, and controls the mass ratio of Al to Mn to Be 1: 1.5-1.65, so that the high-strength manganese-aluminum bronze alloy has high comprehensive mechanical properties in a cast state, the tensile strength is greater than or equal to 800MPa, the yield strength is greater than or equal to 430MPa, the elongation is greater than or equal to 18%, and the room-temperature hardness is greater than 230HBW.
Description
Technical Field
The invention relates to an as-cast high-strength manganese-aluminum bronze alloy and a preparation method thereof, belonging to the technical field of copper alloy casting.
Background
With the development of ship technology, the requirements for ship accessories are gradually increased. The ship proposes the materials of the valve body casting: the tensile strength is more than or equal to 800MPa, the yield strength is more than or equal to 430MPa, and meanwhile, the elongation of the alloy is more than or equal to 18 percent, and the hardness is more than or equal to 230HBW. However, the technical index far exceeds the national technical requirement, the existing cast high manganese aluminum bronze can not meet the requirement, and a new high-strength manganese aluminum nickel bronze material is urgently needed.
The comprehensive performance of the high manganese aluminum nickel bronze can meet the technical requirements, and the high manganese aluminum nickel bronze is mainly used for propellers, valve bodies, pump bodies and the like of ships.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an as-cast high-strength manganese aluminum bronze alloy and a preparation method thereof, wherein the alloy has high strength and excellent comprehensive mechanical properties. On the premise of ensuring that the elongation of the material is not changed, the tensile strength, the yield strength and the hardness of the material are greatly improved.
In order to achieve the purpose, the invention provides an as-cast high-strength manganese aluminum bronze alloy which comprises the following components in parts by weight:
an as-cast high strength manganese aluminum bronze alloy consisting of, in mass percent, 12.5% to 13.5% Mn,7.8% to 8.3% Al,1.9% to 2.2% Ni,3.0% to 3.3% Fe,0.1% to 0.15% Be, less than or equal to 0.01% Zn, less than or equal to 0.01% C, the mass ratio of Al to Mn being 1:1.55 to 1.65, and the balance of Cu.
Preferably, the as-cast high-strength manganese-aluminum bronze alloy comprises the following components in percentage by mass: 12.55% Mn,8.1% by weight Al,1.93% by weight Ni,3.1% by weight Fe,0.12% by weight Be, ≦ 0.01% by weight Zn, ≦ 0.01% by weight C, the mass ratio of Al to Mn being 1:1.55 and the balance of Cu.
The invention provides a preparation method of as-cast high-strength manganese-aluminum bronze alloy, which comprises the following steps: 1) Melting the raw materials under the protection of a covering agent; 2) Deoxidizing the alloy liquid by using a deoxidizer containing rare earth; 3) Refining the alloy liquid by using a refining agent; 4) Casting in a standard metal mold to obtain the product.
The melting in the step 1) is to mix the raw materials, firstly add a copper block to lay a bottom at the bottom of the crucible, then add electrolytic manganese, a metallic nickel block, common carbon steel, metallic aluminum and QBe2.0 beryllium bronze, then fill the crucible with electrolytic copper, and add the rest electrolytic copper after the raw materials are completely melted at 1300-1350 ℃.
In the step 2), the deoxidizer packaged by the aluminum foil is pressed into the bottom of the molten metal by a pressing spoon for deoxidation, the deoxidation treatment temperature is 1200 +/-10 ℃, the treatment time is 3-5 min, and the mass fraction of the deoxidizer is 0.1%.
The refining treatment in the step 3) is to press the refining agent wrapped by the aluminum foil into the bottom of the molten copper by a pressing spoon, stir the mixture along the bottom of the crucible in the same direction, and treat the mixture at 1230 +/-10 ℃ for 3-5 min.
The pouring temperature in the step 4) is 1120-1150 ℃.
The invention provides a preparation method of an as-cast high-strength manganese-aluminum bronze alloy, which comprises the following steps:
(1) The smelting furnace is selected from a statically heated oil furnace, a gas furnace or a coke furnace, and the crucible is selected from a silicon carbide graphite composite crucible;
(2) The raw materials are electrolytic copper, electrolytic manganese, metallic nickel, carbon steel, metallic aluminum and QBe2.0 beryllium bronze rod;
(3) The auxiliary material deoxidizer is selected from a No. 1 deoxidizer tube produced by Jin Yida metallurgy materials of south China sea in Foshan city, the refining agent is selected from a commercial aluminum bronze refining agent produced by Ningbo ding Innovation materials of Co., ltd, and the covering agent is selected from dehydrated charcoal particles or graphite flakes;
(4) Cleaning a graphite crucible before smelting to prevent other residual elements from entering alloy liquid;
(5) Firstly, 50 percent of covering agent and 50 percent of refining agent are put into the bottom of a crucible;
(6) Adding an electrolytic copper block at the bottom of the crucible, wherein the thickness is not less than 200mm, so that electrolytic manganese added subsequently is prevented from being accumulated at the bottom of the crucible and not easy to melt;
(7) Putting all metal nickel blocks on the laid electrolytic copper, and then putting carbon steel and QBe2.0 beryllium bronze rods;
(8) Putting 1-2 layers of electrolytic copper plates close to the inner wall of the crucible, adding electrolytic manganese at the middle position, and finally adding metal aluminum;
(9) Sealing the smelting furnace, starting heating, opening a furnace cover when the temperature of the smelting furnace rises to 200 ℃, and adding the residual covering agent;
(10) Rapidly heating to 1300-1350 ℃, and gradually adding the rest dried electrolytic copper plate when the electrolytic manganese and the carbon steel are completely melted;
(11) Adjusting the furnace temperature to 1200 plus or minus 10 ℃, and keeping the temperature for 10 minutes;
(12) Pressing the packed deoxidizing tube into the bottom of the alloy liquid by using a pressing spoon, and rotating the pressing spoon around the inner wall of the crucible for 3-5 minutes;
(13) After the deoxidation is finished, the temperature of the metal liquid is raised to 1250 +/-10 ℃, the metal liquid is refined after being kept warm for 10 minutes, the remaining 50 percent of refining agent is pressed into the bottom of the alloy liquid, the pressing spoon rotates around the inner wall of the crucible, and the refining time is 5 minutes; (14) After refining, the temperature of the metal liquid is increased to 1200 +/-10 ℃, the metal liquid is taken out of the furnace for casting after heat preservation for 10 minutes, the casting temperature is 1120-1150 ℃, a metal mold for casting a sample is used, the mold material selected in the project is HT250, and the mold temperature is 30-50 ℃.
Compared with the prior art, the invention has the following advantages:
various mechanical properties of the hydraulic coupler casting produced by the method reach performance indexes, and the localization of the product is successfully realized.
The highest water pressure resistance of the high-pressure-resistant valve body casting produced by the method is 60MPa, the highest air pressure resistance of the high-pressure-resistant valve body casting is 40MPa, and the high-pressure-resistant valve body casting is installed and used to obtain a good effect.
The specific implementation mode is as follows:
in order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below.
Example 1
(1) Cleaning a graphite crucible, and putting 0.5Kg of dehydrated charcoal particles and 0.5Kg of refining agent at the bottom of the crucible; raw materials according to mass percent of 13.2% Mn, 8.2% Al, 3.2% Fe, 2.0% Ni, QBe2.0 beryllium bronze 5.8%, balance Cu, compounding 500Kg;
(2) Preparing 100g of a deoxygenation pipe, 1Kg of a refining agent and 1Kg of dehydrated charcoal particles according to the mass of auxiliary materials;
(3) Paving a layer of electrolytic copper with thickness of about 200mm at the bottom of the crucible, and then sequentially adding Ni, fe, QBe2.0, mn, al and part of copper;
(4) Closing the furnace cover, heating to 200 ℃, and adding the rest covering agent;
(5) Rapidly heating to 1300-1350 ℃, and preserving heat for 15 minutes;
(6) Stirring the molten metal by using a graphite stick, and judging whether the carbon steel and the electrolytic manganese are completely molten or not;
(7) After the molten metal in the crucible is melted down, adding the residual electrolytic copper for cooling;
(8) Keeping the temperature at 1200 +/-10 ℃ for 10 minutes, and carrying out deoxidation treatment for 3-5 minutes until the metal liquid level does not roll;
(9) Raising the furnace temperature to 1250 +/-10 ℃, preserving the temperature for 10 minutes, and refining the metal liquid for 3 to 5 minutes until the metal liquid level does not roll;
(10) And (3) increasing the furnace temperature to 1200 +/-10 ℃, keeping the temperature for 10 minutes, discharging from the furnace, casting, and casting 5 metal type mechanical samples along with the furnace.
The chemical composition and mechanical properties of this example are shown in table 1.
Table 1 example 1 results of physical and chemical examination
Example 2
(1) Cleaning a graphite crucible, and putting 0.5Kg of dehydrated charcoal particles and 0.5Kg of refining agent at the bottom of the crucible;
(2) Raw materials according to mass percent of 13.5% Mn, 8.0% Al, 3.3% Fe, 2.0% Ni, QBe2.0 beryllium bronze 5.8%, balance Cu, compounding 500Kg;
(3) Preparing 100g of a deoxygenation pipe, 1Kg of a refining agent and 1Kg of dehydrated charcoal particles according to the mass of auxiliary materials;
(4) Paving a layer of electrolytic copper with thickness of about 200mm at the bottom of the crucible, and then sequentially adding Ni, fe, QBe2.0, mn, al and part of copper;
(5) Closing the furnace cover, heating to 200 ℃, and adding the rest covering agent;
(6) Rapidly heating to 1300-1350 ℃, and preserving heat for 15 minutes;
(7) Stirring the molten metal by using a graphite rod, and judging whether the carbon steel and the electrolytic manganese are completely molten or not;
(8) After the molten metal in the crucible is melted down, adding the residual electrolytic copper for cooling;
(9) Keeping the temperature at 1200 +/-10 ℃ for 10 minutes, and carrying out deoxidation treatment for 3-5 minutes until the metal liquid level does not roll;
(10) Raising the furnace temperature to 1250 +/-10 ℃, preserving the temperature for 10 minutes, and refining the metal liquid for 3 to 5 minutes until the metal liquid level does not roll;
(11) Raising the furnace temperature to 1200 +/-10 ℃, preserving the temperature for 10 minutes, discharging and casting 4 circular ring centrifugal castings with the outer diameter of 290mm, the inner diameter of 170mm and the height of 170mm, and casting 5 metal mold mechanical samples along with the furnace;
(12) And (5) carrying out body performance inspection on one of the circular ring castings.
The chemical composition and mechanical properties of this example are shown in table 2.
Table 2 example 2 results of physical and chemical examination
Example 3
(1) Cleaning a graphite crucible, and putting 0.5Kg of dehydrated charcoal particles and 0.5Kg of refining agent at the bottom of the crucible;
(2) The raw materials are divided into 14.0% by mass of Mn, 8.0% by mass of Al, 3.3% by mass of Fe, 2.1% by mass of Ni, 5.8% by mass of QBe2.0% by mass of beryllium bronze, and the balance of Cu, and are mixed for 500Kg;
(3) Preparing 100g of a deoxygenation pipe, 1Kg of a refining agent and 1Kg of dehydrated charcoal particles according to the mass of auxiliary materials;
(4) Paving a layer of electrolytic copper with thickness of about 200mm at the bottom of the crucible, and then sequentially adding Ni, fe, QBe2.0, mn, al and part of copper;
(5) Closing the furnace cover, heating to 200 ℃, and adding the rest covering agent;
(6) Rapidly heating to 1300-1350 ℃, and preserving heat for 15 minutes;
(7) Stirring the molten metal by using a stone grinding rod, and judging whether the carbon steel and the electrolytic manganese are completely molten or not;
(8) After the molten metal in the crucible is melted down, adding the residual electrolytic copper for cooling;
(9) Keeping the temperature at 1200 +/-10 ℃ for 10 minutes, and carrying out deoxidation treatment for 3-5 minutes until the metal liquid level does not roll;
(10) Raising the furnace temperature to 1250 +/-10 ℃, preserving the heat for 10 minutes, and refining for 3-5 minutes until the metal liquid level does not roll;
(11) And (3) increasing the furnace temperature to 1200 +/-10 ℃, preserving the temperature for 10 minutes, discharging and casting 8 high-pressure-resistant valve body castings, and casting 5 metal mechanical samples along with the furnace. The chemical composition and mechanical properties of this example are shown in table 3.
Table 3 results of physical and chemical examination of example 3
Claims (4)
1. The as-cast high-strength manganese-aluminum bronze alloy is characterized by comprising the following components in percentage by mass of 12.5-13.5% of Mn, 7.8-8.3% of Al, 1.9-2.2% of Ni, 3.0-3.3% of Fe, 0.1-0.15% of Be, 0-0.01% of Zn, 0-0.01% of C, and the mass ratio of Al to Mn is 1: 1.55-1.65, and the balance of Cu;
the preparation method of the alloy comprises the following steps:
1) Melting the raw materials under the protection of a covering agent, wherein the melting is to mix the raw materials, firstly adding a copper block and the covering agent to lay a bottom at the bottom of a crucible, then adding electrolytic manganese, a metallic nickel block, common carbon steel, metallic aluminum and QBe2.0 beryllium bronze, then filling the crucible with electrolytic copper, and after the raw materials are completely melted at 1300-1350 ℃, adding the rest of the electrolytic copper and the covering agent;
2) Deoxidizing the alloy liquid by using a rare earth-containing deoxidizer, wherein the mass fraction of the deoxidizer is 0.1%, pressing the deoxidizer packaged by an aluminum foil into the bottom of the metal liquid by using a pressing spoon, and deoxidizing at the temperature of 1200 +/-10 ℃ for 3-5 min;
3) Refining the alloy liquid by using a refining agent;
4) And casting in a standard metal mold to obtain the product.
2. The as-cast high-strength manganese aluminum bronze alloy according to claim 1, which is composed of the following components in percentage by mass: 12.55% of Mn,8.1% of Al,1.93% of Ni,3.1% of Fe,0.12% of Be, 0-0.01% of Zn, 0-0.01% of C, and the mass ratio of Al to Mn is 1:1.55 and the balance of Cu.
3. The as-cast high-strength manganese aluminum bronze alloy according to claim 1, wherein the refining treatment in step 3) is carried out by pressing the refining agent wrapped with aluminum foil into the bottom of molten copper with a pressing spoon and stirring the mixture in the same direction along the bottom of a crucible at a treatment temperature of 1230 +/-10 ℃ for 3-5 min.
4. The as-cast high-strength manganese aluminum bronze alloy according to claim 1, wherein the casting temperature in step 4) is 1120-1150 ℃.
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| CN104357708A (en) * | 2014-11-12 | 2015-02-18 | 中船重工西安东仪科工集团有限公司 | Environment-friendly safe melting process method of high-performance nickel-aluminum bronze |
| WO2017020645A1 (en) * | 2015-07-31 | 2017-02-09 | 广东欧珀移动通信有限公司 | Electronic device, die-casting aluminium alloy, and preparation method for die-casting aluminium alloy |
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