CN112210691A - Corrosion-resistant copper alloy and preparation method thereof - Google Patents
Corrosion-resistant copper alloy and preparation method thereof Download PDFInfo
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- 230000007797 corrosion Effects 0.000 title claims abstract description 72
- 238000005260 corrosion Methods 0.000 title claims abstract description 72
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000956 alloy Substances 0.000 claims abstract description 79
- 238000003723 Smelting Methods 0.000 claims abstract description 77
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 72
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000010949 copper Substances 0.000 claims abstract description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 25
- 239000000155 melt Substances 0.000 claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 21
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 claims abstract description 21
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 21
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 21
- 229910001122 Mischmetal Inorganic materials 0.000 claims abstract description 20
- 238000009750 centrifugal casting Methods 0.000 claims abstract description 17
- 238000001125 extrusion Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000011572 manganese Substances 0.000 claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 10
- 238000001192 hot extrusion Methods 0.000 claims abstract description 7
- 239000011889 copper foil Substances 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 24
- 238000005266 casting Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- 229910002065 alloy metal Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000003610 charcoal Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002893 slag Substances 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000498 cooling water Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 239000010705 motor oil Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C22C9/06—Alloys based on copper with nickel or cobalt 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
-
- 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
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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
本发明公开了一种耐蚀铜合金及其制备方法，包括：对电解铜板、电解镍板、铝板、铜铁中间合金、铜锰中间合金及混合稀土进行预处理，混合稀土为La、Ce的混合物；称取原料，使上述组分的质量百分含量为Ni 6‑8％、Al 3‑7％、Fe 1‑1.6％、Mn 0.4‑1％及混合稀土0.032‑0.045％，余量为Cu，La的百分含量为35‑45％；依次将电解铜板、电解镍板、铜铁中间合金、铜锰中间合金、铜箔包裹的混合稀土放入熔炉中进行一次熔炼，熔炼除渣后向熔炉加入铝板进行二次熔炼；将熔体浇注到离心铸造机中进行冷却凝固成坯料，并进行加工处理后得到耐蚀铜合金铸锭；加热保温后放入挤压模具进行热挤压变形加工，得到耐蚀铜合金。The invention discloses a corrosion-resistant copper alloy and a preparation method thereof. mixture; Weigh the raw materials so that the mass percentages of the above-mentioned components are Ni 6-8%, Al 3-7%, Fe 1-1.6%, Mn 0.4-1% and mischmetal 0.032-0.045%, and the balance is The percentage content of Cu and La is 35-45%; the electrolytic copper plate, electrolytic nickel plate, copper-iron master alloy, copper-manganese master alloy, and mixed rare earth wrapped in copper foil are put into the furnace for one smelting, and after smelting and slag removal Add aluminum plates to the furnace for secondary smelting; pour the melt into a centrifugal casting machine to cool and solidify into a billet, and process it to obtain a corrosion-resistant copper alloy ingot; heat and keep warm and put it into an extrusion die for hot extrusion deformation processing to obtain a corrosion-resistant copper alloy.
Description
Technical Field
The invention belongs to the technical field of alloy materials, relates to a corrosion-resistant copper alloy and further relates to a preparation method of the corrosion-resistant copper alloy.
Background
Copper and its alloy have high strength, good corrosion resistance and antimicrobial corrosion, so that they are widely used in the fields of ship manufacture, ocean engineering, seawater chemical engineering, etc., and are mainly used in ship shells, various wires, pump bodies, valve bodies, ship propellers, seawater desalination, ship condenser pipes, etc. But due to the particularities of the ocean, copper and its alloys are often severely corroded.
At present, most of corrosion-resistant copper alloys researched and applied at home and abroad mainly comprise brass, tin bronze, B10(Cu-10Ni-1Fe-1Mn), B30(Cu-30Ni-1Fe-lMn) and the like, however, the service conditions of the corrosion-resistant copper alloys are increasingly severe due to complex and changeable marine conditions, the safety and reliability requirements of key parts are higher and higher, and the traditional corrosion-resistant copper alloys cannot meet the use requirements of high-end fields.
The patent (publication number: CN102776410A, name: a corrosion-resistant copper alloy) discloses a corrosion-resistant copper alloy, which uses a large amount of tin, scandium and titanium with high equivalent and a large amount of low-potential metal materials such as magnesium and zinc, and has complex composition of alloy elements, increased production and synthesis difficulty and limited popularization and application range.
Disclosure of Invention
The invention aims to provide a corrosion-resistant copper alloy, which solves the problem of complex composition of copper alloy elements in the prior art.
The technical scheme adopted by the invention is that the corrosion-resistant copper alloy comprises the following components in percentage by mass: 6-8% of Ni, 3-7% of Al, 1-1.6% of Fe, 0.4-1% of Mn and 0.032-0.045% of misch metal; the balance of Cu, the mixed rare earth is a mixture of La and Ce, and the percentage content of La is 35-45%.
The invention is also characterized in that:
fe. The total percentage of Mn is 2%.
Another object of the present invention is to provide a corrosion-resistant copper alloy, which solves the problem of complex composition of copper alloy elements in the prior art.
The other technical scheme adopted by the invention is that the preparation method of the corrosion-resistant copper alloy comprises the following steps:
step 1, pretreating an electrolytic copper plate, an electrolytic nickel plate, an aluminum plate, a copper-iron intermediate alloy, a copper-manganese intermediate alloy and mixed rare earth, wherein the mixed rare earth is a mixture of La and Ce;
step 2, weighing the pretreated electrolytic copper plate, electrolytic nickel plate, aluminum plate, copper-iron intermediate alloy, copper-manganese intermediate alloy and misch metal, wherein the components comprise, by mass, 6-8% of Ni, 3-7% of Al, 1-1.6% of Fe, 0.4-1% of Mn and 0.032-0.045% of misch metal, the balance being Cu, and the percentage content of La is 35-45%;
step 3, sequentially putting an electrolytic copper plate, an electrolytic nickel plate, a copper-iron intermediate alloy, a copper-manganese intermediate alloy and mixed rare earth into a smelting furnace for primary smelting, and adding an aluminum plate into the smelting furnace for secondary smelting after smelting and deslagging;
step 4, when the melt after the secondary smelting reaches the centrifugal casting condition, pouring the melt into a centrifugal casting machine for cooling and solidifying into a blank, and processing to obtain a corrosion-resistant copper alloy cast ingot;
and 5, firstly, placing the corrosion-resistant copper alloy ingot in a resistance furnace for heating and heat preservation, and then placing the corrosion-resistant copper alloy ingot after heating and heat preservation into an extrusion die for hot extrusion deformation processing to obtain the corrosion-resistant copper alloy.
The step 3 comprises the following specific steps:
firstly, sequentially putting an electrolytic copper plate and an electrolytic nickel plate into a smelting furnace to be smelted to obtain first alloy liquid, and then adding a covering agent to cover the first alloy liquid; when the temperature reaches 1150-1200 ℃, sequentially adding a copper-iron intermediate alloy, a copper-manganese intermediate alloy and a misch metal to finish one-time smelting, and adding the next one after each raw material is molten in the feeding process; after the temperature is raised to 1250-1300 ℃, adding an aluminum plate into the smelting furnace after smelting and deslagging, and uniformly stirring for secondary smelting; and adding a deoxidizer in the primary smelting and the secondary smelting, wherein the time of the primary smelting and the secondary smelting is 35-45 min.
The covering agent is one or a mixture of calcined charcoal and plant ash.
The deoxidizer is magnesium or phosphorus copper, and the dosage of the deoxidizer is 0.6-1.2% of the total weight of the melt.
In the step 4: the centrifugal casting condition is that the melt after secondary smelting reaches 1250-1300 ℃, no scum appears on the surface of the melt, and the melt on the surface is pulled open to form a mirror surface.
The preheating temperature of the casting mold of the centrifugal casting machine is 300-450 ℃, the pouring temperature is 1250-.
The heating and heat preservation temperature in the resistance furnace is 1000-1100 ℃, and the heat preservation time is 1-1.5 h; the preheating temperature of the extrusion die is 500-550 ℃.
The invention has the beneficial effects that:
according to the corrosion-resistant copper alloy, the Ni element can improve the corrosion potential and passivation capability and enhance the corrosion resistance of the alloy; al can form a tough and compact protective film on the surface of the alloy, so that the surface activity is reduced, and the erosion resistance of the alloy is enhanced; fe. Mn can obviously improve the strength and the impact corrosion resistance, and W isFe+WMn2%, the alloy strength and the corrosion resistance are improved optimally; the rare earth can purify the alloy matrix, reduce impurities, refine alloy grains, inhibit the diffusion of copper ions in an oxide layer, reduce the corrosion rate of the alloy and improve the corrosion resistance. According to the preparation method of the corrosion-resistant copper alloy, the obtained corrosion-resistant copper alloy is uniform in structure and components and few in as-cast state defects, and the problems that the traditional corrosion-resistant copper alloy is complex in elements and high in production cost are solved; by utilizing the synergistic effect of various microalloyed elements, the novel high-strength corrosion-resistant copper alloy with low Ni content (Al replaces a small amount of Ni), excellent mechanical property and excellent corrosion resistance is obtained.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The corrosion-resistant copper alloy comprises the following components in percentage by mass: 6-8% of Ni, 3-7% of Al, 1-1.6% of Fe, 0.4-1% of Mn and 0.032-0.045% of misch metal; the balance of Cu, the mixed rare earth is a mixture of La and Ce, and the percentage content of La is 35-45%. Fe. The total percentage of Mn is 2%.
A preparation method of a corrosion-resistant copper alloy specifically comprises the following steps:
step 1, carrying out corresponding oil removal, rust removal and drying treatment on an electrolytic copper plate, an electrolytic nickel plate, an aluminum plate, a copper-iron intermediate alloy, a copper-manganese intermediate alloy and mixed rare earth; the mixed rare earth is a mixture of La and Ce;
step 2, weighing the pretreated electrolytic copper plate, electrolytic nickel plate, aluminum plate, copper-iron intermediate alloy, copper-manganese intermediate alloy and misch metal, wherein the components comprise, by mass, 6-8% of Ni, 3-7% of Al, 1-1.6% of Fe, 0.4-1% of Mn and 0.032-0.045% of misch metal, and the balance of Cu and inevitable impurity components, and the percentage content of La is 35-45%;
step 3, in a micro-oxidation atmosphere, sequentially putting an electrolytic copper plate and an electrolytic nickel plate into a smelting furnace to be smelted to obtain first alloy liquid, and then adding calcined charcoal and plant ash which are dried at about 200 ℃ to cover the first alloy liquid so as to isolate most air and reduce oxidation in the smelting process; when the temperature reaches 1150-1200 ℃, adding a copper-iron intermediate alloy, a copper-manganese intermediate alloy and mixed rare earth wrapped by copper foil in sequence to finish one-time smelting, and adding the next one after each raw material is molten in the feeding process; after the temperature is raised to 1250-1300 ℃, adding an aluminum plate into the smelting furnace after smelting and deslagging, uniformly stirring, and carrying out secondary smelting to obtain a second alloy liquid; the time of primary smelting and secondary smelting is 35-45 min, and a deoxidizer is added in the primary smelting and secondary smelting processes. And in the whole smelting process, the graphite rods are selected for uniform stirring, and the slag removing rods are used for removing slag.
The deoxidizer is magnesium or phosphorus copper, and the dosage of the deoxidizer is 0.6-1.2% of the weight of the second alloy liquid.
Step 4, preheating the casting mold to 300-450 ℃ in advance, when the melt after secondary smelting reaches 1250-1300 ℃, no floating slag appears on the surface of the melt and the surface melt is in a mirror surface shape after being pulled open, standing for 2-3 min, and then pouring the second alloy liquid into a centrifugal casting machine with water cooling through a pouring ladle, wherein the pouring temperature of the centrifugal casting machine is 1250-1300 ℃, and the rotating speed of the centrifugal machine is 1150-1250 rad/min; and (3) cooling the casting mold by introducing water, spraying cooling water on the annular outer wall of the casting mold, cooling and solidifying the casting mold into a blank, and performing turning processing and other treatment to obtain the corrosion-resistant copper alloy ingot.
Step 5, placing the corrosion-resistant copper alloy ingot in a box-type resistance furnace at the temperature of 1000-1100 ℃ for heating and heat preservation for 1-1.5 h; and then preheating an extrusion die to 500-550 ℃, and putting the corrosion-resistant copper alloy ingot after heating and heat preservation into the extrusion die for hot extrusion deformation processing to obtain the corrosion-resistant copper alloy. The lubricant used in the extrusion die is asphalt or a graphite engine oil mixture.
Example 1
Step 1, carrying out corresponding oil removal, rust removal and drying treatment on an electrolytic copper plate, an electrolytic nickel plate, an aluminum plate, a copper-iron intermediate alloy, a copper-manganese intermediate alloy and mixed rare earth; the mixed rare earth is a mixture of La and Ce;
step 2, weighing the pretreated electrolytic copper plate, electrolytic nickel plate, aluminum plate, copper-iron intermediate alloy, copper-manganese intermediate alloy and misch metal, wherein the components comprise, by mass, Ni 7%, Al 3%, Fe 1.2%, Mn 0.8% and misch metal 0.032%, and the balance of Cu and inevitable impurity components, and the percentage content of La is 35%;
step 3, in a micro-oxidation atmosphere, sequentially putting an electrolytic copper plate and an electrolytic nickel plate into a smelting furnace to be smelted to obtain a first alloy liquid, and then adding a mixture of calcined charcoal and plant ash which are dried at about 200 ℃ to cover the first alloy liquid; when the temperature reaches 1150 ℃, adding the copper-iron intermediate alloy, the copper-manganese intermediate alloy and the mixed rare earth wrapped by the copper foil in sequence to finish primary smelting; after the temperature is raised to 1250 ℃, adding an aluminum plate into the smelting furnace after smelting and deslagging, and uniformly stirring for secondary smelting to obtain a second alloy liquid; the time of primary smelting and secondary smelting is 35min, magnesium is added as a deoxidizer in the primary smelting and secondary smelting processes, and the dosage of the magnesium is 0.6 percent of the weight of the second alloy liquid.
Step 4, preheating the casting mold to 300 ℃ in advance, when the melt after secondary smelting reaches 1250 ℃, no scum appears on the surface of the melt and the melt on the surface is in a mirror surface shape, standing for 2min, and then pouring the second alloy liquid into a water-cooled centrifugal casting machine through a pouring ladle, wherein the pouring temperature of the centrifugal casting machine is 1250 ℃, and the rotating speed of the centrifugal machine is 1150 rad/min; and (3) cooling the casting mold by introducing water, spraying cooling water on the annular outer wall of the casting mold, cooling and solidifying the casting mold into a blank, and performing turning processing and other treatment to obtain the corrosion-resistant copper alloy ingot.
Step 5, putting the corrosion-resistant copper alloy ingot in a box-type resistance furnace at 1000 ℃ for heating and heat preservation for 1 h; and then preheating an extrusion die to 500 ℃, and putting the corrosion-resistant copper alloy cast ingot subjected to heating and heat preservation into the extrusion die for hot extrusion deformation processing to obtain the corrosion-resistant copper alloy. The lubricant used in the extrusion die is a graphite engine oil mixture.
Example 2
Step 1, carrying out corresponding oil removal, rust removal and drying treatment on an electrolytic copper plate, an electrolytic nickel plate, an aluminum plate, a copper-iron intermediate alloy, a copper-manganese intermediate alloy and mixed rare earth; the mixed rare earth is a mixture of La and Ce;
step 2, weighing the pretreated electrolytic copper plate, electrolytic nickel plate, aluminum plate, copper-iron intermediate alloy, copper-manganese intermediate alloy and misch metal, wherein the components comprise, by mass, Ni 7%, Al 5%, Fe 1.2%, Mn 0.8% and misch metal 0.045%, and the balance of Cu and inevitable impurity components, and the percentage content of La is 45%;
step 3, in a micro-oxidation atmosphere, sequentially putting an electrolytic copper plate and an electrolytic nickel plate into a smelting furnace to be smelted to obtain a first alloy liquid, and then adding a mixture of calcined charcoal and plant ash which are dried at about 200 ℃ to cover the first alloy liquid; when the temperature reaches 1180 ℃, adding the copper-iron intermediate alloy, the copper-manganese intermediate alloy and the mixed rare earth wrapped by the copper foil in sequence to finish primary smelting; after the temperature is raised to 1280 ℃, adding an aluminum plate into the smelting furnace after smelting and deslagging, uniformly stirring, and carrying out secondary smelting to obtain a second alloy liquid; the time of primary smelting and secondary smelting is 45min, magnesium is added as a deoxidizer in the primary smelting and secondary smelting processes, and the dosage of the magnesium is 1.2 percent of the weight of the second alloy liquid.
Step 4, preheating the casting mold to 450 ℃ in advance, when the melt after secondary smelting reaches 1280 ℃, no scum appears on the surface of the melt and the surface melt is in a mirror surface shape after being pulled open, and after standing for 3min, pouring the second alloy liquid into a water-cooled centrifugal casting machine through a pouring ladle, wherein the pouring temperature of the centrifugal casting machine is 1280 ℃, and the rotating speed of the centrifugal machine is 1250 rad/min; and (3) cooling the casting mold by introducing water, spraying cooling water on the annular outer wall of the casting mold, cooling and solidifying the casting mold into a blank, and performing turning processing and other treatment to obtain the corrosion-resistant copper alloy ingot.
Step 5, putting the corrosion-resistant copper alloy ingot in a box-type resistance furnace at 1100 ℃ for heating and heat preservation for 1.5 h; and then preheating an extrusion die to 550 ℃, and putting the corrosion-resistant copper alloy cast ingot after heating and heat preservation into the extrusion die for hot extrusion deformation processing to obtain the corrosion-resistant copper alloy. The lubricant used in the extrusion die is a graphite engine oil mixture.
Example 3
Step 1, carrying out corresponding oil removal, rust removal and drying treatment on an electrolytic copper plate, an electrolytic nickel plate, an aluminum plate, a copper-iron intermediate alloy, a copper-manganese intermediate alloy and mixed rare earth; the mixed rare earth is a mixture of La and Ce;
step 2, weighing the pretreated electrolytic copper plate, electrolytic nickel plate, aluminum plate, copper-iron intermediate alloy, copper-manganese intermediate alloy and misch metal, wherein the components comprise, by mass, Ni 7%, Al 7%, Fe 1.2%, Mn 0.8% and misch metal 0.038%, and the balance of Cu and inevitable impurity components, and the percentage content of La is 40%;
step 3, in a micro-oxidation atmosphere, sequentially putting an electrolytic copper plate and an electrolytic nickel plate into a smelting furnace to be smelted to obtain a first alloy liquid, and then adding a mixture of calcined charcoal and plant ash which are dried at about 200 ℃ to cover the first alloy liquid; when the temperature reaches 1200 ℃, adding the copper-iron intermediate alloy, the copper-manganese intermediate alloy and the mixed rare earth wrapped by the copper foil in sequence to finish primary smelting; after the temperature is raised to 1300 ℃, adding an aluminum plate into the smelting furnace after smelting and deslagging, and uniformly stirring for secondary smelting to obtain a second alloy liquid; the time of primary smelting and secondary smelting is 40min, magnesium is added as a deoxidizer in the primary smelting and secondary smelting processes, and the dosage of the magnesium is 0.8 percent of the weight of the second alloy liquid.
Step 4, preheating the casting mold to 400 ℃ in advance, when the melt after secondary smelting reaches 1300 ℃, no scum appears on the surface of the melt and the melt on the surface of the melt is in a mirror surface shape, standing for 2min, and then pouring the second alloy liquid into a water-cooled centrifugal casting machine through a pouring ladle, wherein the pouring temperature of the centrifugal casting machine is 1300 ℃, and the rotating speed of the centrifugal machine is 1200 rad/min; and (3) cooling the casting mold by introducing water, spraying cooling water on the annular outer wall of the casting mold, cooling and solidifying the casting mold into a blank, and performing turning processing and other treatment to obtain the corrosion-resistant copper alloy ingot.
Step 5, putting the corrosion-resistant copper alloy cast ingot into a box-type resistance furnace at 1075 ℃ for heating and heat preservation for 1.2 h; and then preheating an extrusion die to 550 ℃, and putting the corrosion-resistant copper alloy cast ingot after heating and heat preservation into the extrusion die for hot extrusion deformation processing to obtain the corrosion-resistant copper alloy. The lubricant used in the extrusion die is a graphite engine oil mixture.
The high-strength corrosion-resistant copper alloy prepared in the embodiments 1 to 3 is subjected to mechanical property and corrosion resistance tests, and the test results are as follows:
| numbering | Corrosion rate, mm/a | Tensile strength, MPa | Elongation percentage |
| Example 1 | 0.0032 | 705 | 28 |
| Example 2 | 0.0035 | 711 | 25 |
| Example 3 | 0.0024 | 724 | 27 |
Through the mode, the tensile strength of the corrosion-resistant copper alloy is over 700MPa, the elongation is over 20 percent, and the alloy has good mechanical property; the corrosion-resistant copper alloy has excellent corrosion resistance, the corrosion rate of 240h is lower than 0.004mm/a, and the corrosion-resistant copper alloy has the advantages of uniform tissue components, few as-cast defects, relatively simple alloy elements, low cost, excellent mechanical property, excellent corrosion resistance and the like, and meets the use requirements of the corrosion-resistant copper alloy under severe service conditions.
Claims (9)
1. The corrosion-resistant copper alloy is characterized by comprising the following components in percentage by mass: 6-8% of Ni, 3-7% of Al, 1-1.6% of Fe, 0.4-1% of Mn and 0.032-0.045% of misch metal; the balance of Cu, the mixed rare earth is a mixture of La and Ce, and the percentage content of La is 35-45%.
2. A corrosion resistant copper alloy according to claim 1 wherein said total percentage of Fe and Mn is 2%.
3. The preparation method of the corrosion-resistant copper alloy is characterized by comprising the following steps of:
step 1, pretreating an electrolytic copper plate, an electrolytic nickel plate, an aluminum plate, a copper-iron intermediate alloy, a copper-manganese intermediate alloy and a mischmetal, wherein the mischmetal is a mixture of La and Ce;
step 2, weighing the pretreated electrolytic copper plate, electrolytic nickel plate, aluminum plate, copper-iron intermediate alloy, copper-manganese intermediate alloy and mischmetal to ensure that the components comprise, by mass, 6-8% of Ni, 3-7% of Al, 1-1.6% of Fe, 0.4-1% of Mn and 0.032-0.045% of mischmetal, the balance being Cu, and the percentage content of La being 35-45%;
step 3, putting the mixed rare earth wrapped by the electrolytic copper plate, the electrolytic nickel plate, the copper-iron intermediate alloy, the copper-manganese intermediate alloy and the copper foil into a smelting furnace in sequence for primary smelting, and adding an aluminum plate into the smelting furnace for secondary smelting after smelting and deslagging;
step 4, when the melt after the secondary smelting reaches the centrifugal casting condition, pouring the melt into a centrifugal casting machine for cooling and solidifying into a blank, and processing to obtain a corrosion-resistant copper alloy cast ingot;
and 5, firstly, placing the corrosion-resistant copper alloy ingot in a resistance furnace for heating and heat preservation, and then placing the corrosion-resistant copper alloy ingot after heating and heat preservation into an extrusion die for hot extrusion deformation processing to obtain the corrosion-resistant copper alloy.
4. The method for preparing the corrosion-resistant copper alloy according to claim 3, wherein the step 3 comprises the following steps:
firstly, sequentially putting an electrolytic copper plate and an electrolytic nickel plate into a smelting furnace to be smelted to obtain first alloy liquid, and then adding a covering agent to cover the first alloy liquid; when the temperature reaches 1150-1200 ℃, sequentially adding a copper-iron intermediate alloy, a copper-manganese intermediate alloy and a misch metal to finish one-time smelting, and adding the next one after each raw material is molten in the feeding process; after the temperature is raised to 1250-1300 ℃, adding an aluminum plate into the smelting furnace after smelting and deslagging, and uniformly stirring for secondary smelting; and adding a deoxidizer in the primary smelting and the secondary smelting, wherein the time of the primary smelting and the secondary smelting is 35-45 min.
5. The method of claim 4, wherein the covering agent is one or a mixture of calcined charcoal and plant ash.
6. The method of claim 4, wherein the deoxidizer is magnesium or phosphorus copper, and the amount of the deoxidizer is 0.6-1.2% of the total weight of the melt.
7. The method of claim 3, wherein in step 4: the centrifugal casting condition is that the melt after secondary smelting reaches 1250-1300 ℃, no scum appears on the surface of the melt, and the melt on the surface of the melt is pulled out and is in a mirror surface shape.
8. The method for preparing the corrosion-resistant copper alloy according to claim 3, wherein the preheating temperature of the casting mold of the centrifugal casting machine is 300-450 ℃, the pouring temperature is 1250-.
9. The method for preparing the corrosion-resistant copper alloy according to claim 3, wherein the heating and heat-preserving temperature in the resistance furnace is 1000-1100 ℃, and the heat-preserving time is 1-1.5 h; the preheating temperature of the extrusion die is 500-550 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114574718A (en) * | 2022-03-29 | 2022-06-03 | 西北有色金属研究院 | Preparation method of 60NiTi alloy bearing |
| CN115369280A (en) * | 2022-08-20 | 2022-11-22 | 国工恒昌新材料沧州有限公司 | C17460 alloy and preparation process thereof |
| CN116732384A (en) * | 2023-08-08 | 2023-09-12 | 宁波兴业盛泰集团有限公司 | Copper nickel silicon alloy cast ingot and preparation method thereof |
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| CN107779660A (en) * | 2017-11-09 | 2018-03-09 | 河南科技大学 | A kind of high-strength high Vulcan metal and preparation method thereof |
| CN107858555A (en) * | 2017-11-09 | 2018-03-30 | 河南科技大学 | A kind of ocean engineering high-strength high Vulcan metal and preparation method thereof |
| CN110592424A (en) * | 2019-08-31 | 2019-12-20 | 江苏迅达电磁线有限公司 | Novel multi-element high-strength high-corrosion-resistance copper alloy and preparation method thereof |
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| CN106319277A (en) * | 2015-06-19 | 2017-01-11 | 中国科学院金属研究所 | Rare earth corrosion-resistant copper alloy and production technology thereof |
| CN107779660A (en) * | 2017-11-09 | 2018-03-09 | 河南科技大学 | A kind of high-strength high Vulcan metal and preparation method thereof |
| CN107858555A (en) * | 2017-11-09 | 2018-03-30 | 河南科技大学 | A kind of ocean engineering high-strength high Vulcan metal and preparation method thereof |
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| CN115369280A (en) * | 2022-08-20 | 2022-11-22 | 国工恒昌新材料沧州有限公司 | C17460 alloy and preparation process thereof |
| CN116732384A (en) * | 2023-08-08 | 2023-09-12 | 宁波兴业盛泰集团有限公司 | Copper nickel silicon alloy cast ingot and preparation method thereof |
| CN116732384B (en) * | 2023-08-08 | 2023-11-21 | 宁波兴业盛泰集团有限公司 | Copper nickel silicon alloy cast ingot and preparation method thereof |
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