CN111004936A - Preparation method of high-strength and high-corrosion-resistance Cu-Ni-Mn alloy - Google Patents
Preparation method of high-strength and high-corrosion-resistance Cu-Ni-Mn alloy Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 191
- 239000000956 alloy Substances 0.000 title claims abstract description 191
- 229910003286 Ni-Mn Inorganic materials 0.000 title claims abstract description 130
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000011282 treatment Methods 0.000 claims abstract description 109
- 238000005097 cold rolling Methods 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 44
- 238000001192 hot extrusion Methods 0.000 claims abstract description 38
- 238000002844 melting Methods 0.000 claims abstract description 23
- 230000008018 melting Effects 0.000 claims abstract description 23
- 230000006698 induction Effects 0.000 claims abstract description 17
- 239000010949 copper Substances 0.000 claims description 37
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 36
- 229910052802 copper Inorganic materials 0.000 claims description 36
- 238000001125 extrusion Methods 0.000 claims description 32
- 230000032683 aging Effects 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- 239000003607 modifier Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 4
- 244000137852 Petrea volubilis Species 0.000 claims description 2
- 238000003723 Smelting Methods 0.000 claims description 2
- 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 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 40
- 230000007797 corrosion Effects 0.000 abstract description 25
- 238000000227 grinding Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 238000001953 recrystallisation Methods 0.000 description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 238000003754 machining Methods 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 230000010287 polarization Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000005204 segregation Methods 0.000 description 3
- 229910002482 Cu–Ni Inorganic materials 0.000 description 2
- 229910016897 MnNi Inorganic materials 0.000 description 2
- 229910018651 Mn—Ni Inorganic materials 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910017566 Cu-Mn Inorganic materials 0.000 description 1
- 229910017871 Cu—Mn Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/16—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling wire rods, bars, merchant bars, rounds wire or material of like small cross-section
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C23/00—Extruding metal; Impact extrusion
- B21C23/22—Making metal-coated products; Making products from two or more metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
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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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F3/00—Changing the physical structure of non-ferrous metals or alloys by special physical methods, e.g. treatment with neutrons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
- B21B2003/005—Copper or its alloys
Abstract
The invention discloses a preparation method of a high-strength high-corrosion-resistance Cu-Ni-Mn alloy, which comprises the following steps: step 1: preparing a Cu-Ni-Mn alloy ingot by a vacuum induction melting method; step 2: carrying out hot extrusion treatment on the Cu-Ni-Mn alloy cast ingot in the step 1, and then carrying out cold rolling treatment on the hot extruded Cu-Ni-Mn alloy at room temperature; and step 3: and (3) performing electric pulse treatment on the alloy subjected to cold rolling treatment in the step (2) to obtain the high-strength and high-corrosion-resistance Cu-Ni-Mn alloy. The Cu-Ni-Mn alloy prepared by the invention has high strength and high corrosion resistance. The alloy has uniform and fine structure, can simultaneously have excellent comprehensive performance with the strength of 1266.6MPa and the corrosion rate of 0.053mm/year at the highest, and provides important help for subsequent engineering application and scientific research.
Description
Technical Field
The invention belongs to the technical field of multi-element Cu alloy post-treatment, and particularly relates to a preparation method of a high-strength high-corrosion-resistance Cu-Ni-Mn alloy.
Background
The Cu-Ni-Mn alloy used in the submarine oil pipeline and the ship manufacture has good corrosion resistance but only about 300MPa of strength, and the low strength causes the Cu-Ni-Mn alloy to be easily deformed and even broken under the action of external force during work, so that the strength of the Cu-Ni-Mn alloy is improved by means of age strengthening and work hardening at present, however, Mn and Ni atoms can be desolventized from an α -Cu matrix and precipitate in a form of a theta-MnNi phase in the aging process, the Cu-Ni-Mn alloy obviously improves the energy precipitation strength of the Cu-Ni-Mn alloy, and the corrosion resistance of the Cu-Ni-Mn alloy are greatly improved, so that the corrosion resistance of the Cu-Ni-Mn alloy is greatly improved, the corrosion resistance of the Cu-Mn-Ni alloy is greatly improved, the corrosion resistance of the Cu-Ni-Mn alloy is greatly improved, the corrosion resistance of the Cu-Ni alloy is improved, the alloy is greatly improved, and the corrosion resistance of the Cu-Ni alloy is greatly improved, and the alloy is beneficial to the strengthening of the corrosion resistance of the Cu-Mn alloy.
Disclosure of Invention
The invention aims to provide a preparation method of a high-strength high-corrosion-resistance Cu-Ni-Mn alloy, which solves the problem that the Cu-Ni-Mn alloy cannot give consideration to both high strength and high corrosion resistance in the conventional post-treatment mode.
The technical scheme adopted by the invention is that,
a preparation method of a high-strength high-corrosion-resistance Cu-Ni-Mn alloy specifically comprises the following steps:
step 1: preparing a Cu-Ni-Mn alloy ingot by a vacuum induction melting method;
step 2: carrying out hot extrusion treatment on the Cu-Ni-Mn alloy cast ingot in the step 1, and then carrying out cold rolling treatment on the hot extruded Cu-Ni-Mn alloy at room temperature;
and step 3: and (3) performing electric pulse treatment on the alloy subjected to cold rolling treatment in the step (2) to obtain the high-strength and high-corrosion-resistance Cu-Ni-Mn alloy.
The present invention is also characterized in that,
in the step 1, the specific process is as follows: adopting T2 pure copper, adding 20% of electrolytic nickel and 20% of electrolytic manganese, carrying out smelting at 1135-1165 ℃, keeping the temperature for 5-10 min after furnace burden is completely melted, adding a modifier, heating and stirring for 15-20 min, and then pouring by using a water-cooling copper mold to obtain a Cu-Ni-Mn alloy cast ingot.
In the step 1, the alterant is boron powder.
In step 2, the specific process of the hot extrusion treatment is as follows: wrapping a copper sheet with the thickness of 0.5-1 mm on a Cu-Ni-Mn alloy ingot, placing the Cu-Ni-Mn alloy ingot in a nitrogen heating furnace with the heating temperature of 940-960 ℃ for softening treatment, keeping the temperature for 85-95 min, placing the Cu-Ni-Mn alloy ingot in an extrusion cylinder preheated to 395-405 ℃ for hot extrusion treatment after the heat preservation is finished, controlling the extrusion force to be not lower than 3500KN, the extrusion rate to be 20-32 mm/s and the extrusion ratio to be 9:1, and then obtaining the Cu-Ni-Mn alloy test bar.
In the step 2, the specific process of the room temperature cold rolling treatment is as follows: turning the Cu-Ni-Mn alloy test bar subjected to the hot extrusion treatment, and then performing cold rolling treatment on the alloy test bar by using a vertical cold rolling mill at room temperature, wherein the cold rolling direction is performed along the axial direction of the hot extrusion, and the deformation of each part of the alloy is ensured to be uniform and consistent by reciprocating twice in each pass in the deformation process.
In step 3, the specific process of electric pulse treatment is as follows: carrying out aging treatment on the Cu-Ni-Mn alloy plate subjected to cold rolling treatment at room temperature in a resistance furnace at the temperature of 400-450 ℃, wherein the aging time is 65-75 h, then polishing the plate to be bright by using sand paper, and then controlling the root mean square current density to be 9.80 multiplied by 10 by adjusting the pulse voltage and the pulse frequency of an electric pulse power supply6A/m2～1.24×107A/m2And (3) carrying out electric pulse treatment for 140-160 s, and carrying out air cooling after the treatment is finished to obtain the high-strength and high-corrosion-resistance Cu-Ni-Mn alloy.
The preparation method has the advantages that the hot extrusion treatment is carried out on the as-cast Cu-Ni-Mn alloy, the micro segregation in the as-cast structure of the alloy is improved, the alloy is subjected to dynamic recovery recrystallization, the structure is changed from a thick dendrite with poor comprehensive performance to a fine isometric crystal with good comprehensive performance, meanwhile, the cold rolling treatment is combined with the room-temperature cold rolling treatment with large deformation amount, a large number of defects such as dislocation, twin crystal and the like are introduced into the alloy, the strength of the alloy is greatly improved, the resistivity and the internal energy storage of the alloy are obviously improved, good conditions are provided for the subsequent treatment, the cold rolling treatment is favorable for enabling the theta-MnNi precipitate generated in the subsequent aging process of the alloy to be converted from grain boundary precipitation to in-crystal precipitation, the influence of the grain boundary preferential precipitation on the mechanical performance and the corrosion resistance of the alloy is reduced, the aging treatment can enable the Cu-Ni-Mn alloy to generate a large number of theta-Mnni precipitate, the strength of the alloy is continuously improved on the basis of the improvement of the alloy strength of the processing hardening treatment, the grain boundary precipitation can be introduced in a short time, the alloy, the recovery recrystallization of the alloy can be realized, the alloy can be realized by the electrical pulse, the defect that the alloy is not only, the alloy, the defect of the grain recovery recrystallization of the Cu-Ni-Mn-Ni alloy is improved, the alloy can be recovered crystal grain recovery recrystallization rate is improved, the alloy is improved, the alloy is.
Drawings
FIG. 1 is a Tafel plot of the Cu-Ni-Mn alloy of examples 1-5 in a method of preparing a high strength and high corrosion resistance Cu-Ni-Mn alloy according to the present invention;
FIG. 2 is a stress-strain curve of the Cu-Ni-Mn alloy of examples 1 to 5 in the production method of a high-strength high-corrosion resistance Cu-Ni-Mn alloy according to the present invention;
FIG. 3 is a photograph showing the structure of a high-strength high-corrosion resistant Cu-Ni-Mn alloy in example 4 of the production process of a high-strength high-corrosion resistant Cu-Ni-Mn alloy according to the present invention;
FIG. 4 is a Nyquist curve fitted to the Cu-Ni-Mn alloys of examples 1 to 5 in the method for preparing a high-strength high-corrosion resistance Cu-Ni-Mn alloy of the present invention.
Detailed Description
The method for preparing a high-strength and high-corrosion-resistance Cu-Ni-Mn alloy according to the present invention will be described in detail with reference to the accompanying drawings and embodiments.
A preparation method of a high-strength high-corrosion-resistance Cu-Ni-Mn alloy specifically comprises the following steps:
step 1: preparing a Cu-Ni-Mn alloy ingot by a vacuum induction melting method;
step 2: carrying out hot extrusion treatment on the Cu-Ni-Mn alloy cast ingot in the step 1, and then carrying out cold rolling treatment on the hot extruded Cu-Ni-Mn alloy at room temperature;
and step 3: and (3) performing electric pulse treatment on the alloy subjected to cold rolling treatment in the step (2) to obtain the high-strength and high-corrosion-resistance Cu-Ni-Mn alloy.
The method comprises the following specific steps:
step 1: preparing Cu-Ni-Mn alloy by adopting a vacuum induction melting method, mixing pure copper T2, electrolytic nickel and electrolytic manganese according to the proportion of 20% respectively, carrying out melting at 1135-1165 ℃, keeping the temperature for 5-10 min after furnace burden is completely melted, adding a modifier such as boron powder, heating and stirring for 15-20 min, and then pouring by using a water-cooling copper mold to obtain a Cu-Ni-Mn alloy cast ingot.
Step 2: machining the Cu-Ni-Mn alloy subjected to vacuum induction melting into an ingot with the diameter D of 55-62 mm and the length L of 60-350 mm, wrapping a copper sheet with the thickness of 0.5-1 mm, placing the copper sheet in a nitrogen heating furnace with the heating temperature of 940-960 ℃ for softening treatment, keeping the temperature for 85-95 min, immediately placing the copper sheet in an extrusion cylinder preheated to 395-405 ℃ for hot extrusion treatment after the heat preservation is finished, controlling the extrusion force to be not less than 3500KN, controlling the extrusion rate to be 20-32 mm/s and the extrusion ratio to be 9:1, and finally obtaining the hot extrusion Cu-Ni-Mn alloy test bar with the diameter D of 20 mm.
And step 3: turning the Cu-Ni-Mn alloy test bar subjected to the hot extrusion treatment to about 14mm, then performing cold rolling treatment by using a vertical cold rolling mill at room temperature, wherein the cold rolling direction is performed along the hot extrusion axial direction, the final cold rolling thickness of the alloy is controlled to about 3mm in the cold rolling treatment process, and the deformation of each part of the alloy is ensured to be uniform and consistent by reciprocating twice in each pass in the deformation process.
Aging the Cu-Ni-Mn alloy plate subjected to cold rolling at room temperature in a box-type resistance furnace at the temperature of 430 ℃ for 65-75 h, polishing the surface of the alloy plate subjected to aging treatment by using abrasive paper with the granularity of 280-1200 #, completely covering the last abrasive paper polishing mark by the next pass until the surface is polished to be bright,
then controlling the root mean square current density to be 9.80 multiplied by 10 by adjusting the pulse voltage and the pulse frequency of the electric pulse power supply6A/m2～1.24×107A/m2And (4) carrying out electric pulse treatment for 140-160 s, and then carrying out air cooling after the treatment is finished to obtain the high-strength and high-corrosion-resistance Cu-Ni-Mn alloy.
The hot extrusion treatment temperature is higher than the recrystallization temperature of the Cu-Ni-Mn alloy, the treatment process causes the severe dynamic recovery recrystallization of the Cu-Ni-Mn alloy, a large amount of cast coarse dendritic structures are converted into fine isometric crystal structures in the process, the structural uniformity of the alloy is improved, and meanwhile, the component segregation of the alloy is improved.
The invention relates to a preparation method of a high-strength high-corrosion-resistance Cu-Ni-Mn alloy, which adopts a mode of combining multiple processes of vacuum induction melting, hot extrusion treatment, room-temperature cold rolling treatment and electric pulse treatment, changes the structure appearance of the Cu-Ni-Mn alloy in the existing post-treatment mode, and solves the problem that the Cu-Ni-Mn alloy cannot give consideration to both high strength and high corrosion resistance in the existing post-treatment mode. The Cu-Ni-Mn alloy prepared by the method has uniform and fine structure, can simultaneously have excellent comprehensive performance of 1266.6MPa strength and 0.053mm/year corrosion rate at the highest degree, and provides important help for subsequent engineering application and scientific research.
The method for producing a high-strength and high-corrosion-resistance Cu-Ni-Mn alloy according to the present invention will not be described in further detail below with reference to specific examples.
Example 1
A preparation method of a high-strength and high-corrosion-resistance Cu-Ni-Mn alloy adopts a vacuum induction melting method to prepare the Cu-Ni-Mn alloy, adopts T2 pure copper, electrolytic nickel and electrolytic manganese which are proportioned according to a proportion of 20%, the melting temperature is carried out at 1135 ℃, the furnace burden is completely melted, heat is preserved for 10min, modifier boron powder and the like are added, the mixture is heated and stirred for 20min, and then a water-cooled copper mold is used for pouring, so that a Cu-Ni-Mn alloy cast ingot is obtained.
Machining the Cu-Ni-Mn alloy subjected to vacuum induction melting into an ingot with the diameter D of 55mm and the length L of 60mm, wrapping a copper sheet with the thickness of 0.5mm, placing the copper sheet in a nitrogen heating furnace with the heating temperature of 940 ℃ for softening treatment, keeping the temperature for 85min, immediately placing the copper sheet in an extrusion cylinder preheated to 395 ℃ for hot extrusion treatment after the heat preservation is finished, controlling the extrusion force to be 3500KN, controlling the extrusion rate to be 20mm/s and the extrusion ratio to be 9:1, and finally obtaining the hot-extruded Cu-Ni-Mn alloy test bar with the diameter D of 20 mm.
Turning the Cu-Ni-Mn alloy test bar subjected to the hot extrusion treatment to 14mm, and then performing cold rolling treatment by using a vertical cold rolling mill at room temperature, wherein the cold rolling direction is performed along the hot extrusion axial direction, the final cold rolling thickness of the alloy is controlled to be 3mm in the cold rolling treatment process, and the deformation of each part of the alloy is ensured to be uniform and consistent by reciprocating twice in each pass in the deformation process. The obtained cold-rolled Cu-Ni-Mn alloy plate has the strength of 764.5MPa, the self-corrosion potential of-0.100V and the self-corrosion current density of 5.31 multiplied by 10-4A/cm2The corrosion rate is 0.492mm/year, and the polarization resistance is 8.81X 104Ω·cm2。
Example 2
A preparation method of a high-strength and high-corrosion-resistance Cu-Ni-Mn alloy comprises the steps of preparing the Cu-Ni-Mn alloy by a vacuum induction melting method, preparing pure T2 copper, electrolytic nickel and electrolytic manganese according to a proportion of 20%, carrying out melting at 1165 ℃, keeping the temperature for 10min after furnace burden is completely melted, adding modifier boron powder and the like, heating and stirring for 20min, and then pouring by using a water-cooling copper mold to obtain a Cu-Ni-Mn alloy cast ingot.
Machining the Cu-Ni-Mn alloy subjected to vacuum induction melting into an ingot with the diameter D of 62mm and the length L of 350mm, wrapping a copper sheet with the thickness of 1mm, placing the copper sheet in a nitrogen heating furnace with the heating temperature of 960 ℃ for softening treatment, keeping the temperature for 95min, immediately placing the copper sheet in an extrusion cylinder preheated to 405 ℃ in advance for hot extrusion treatment after the heat preservation is finished, controlling the extrusion force of 3600KN, controlling the extrusion rate of 32mm/s and the extrusion ratio of 9:1, and finally obtaining the hot-extruded Cu-Ni-Mn alloy test bar with the diameter D of 20 mm.
Turning the Cu-Ni-Mn alloy test bar subjected to the hot extrusion treatment to 13mm, and then performing cold rolling treatment by using a vertical cold rolling mill at room temperature, wherein the cold rolling direction is performed along the hot extrusion axial direction, the final cold rolling thickness of the alloy is controlled to be 4mm in the cold rolling treatment process, and the deformation of each part of the alloy is ensured to be uniform and consistent by reciprocating twice in each pass in the deformation process.
And (3) carrying out aging treatment on the Cu-Ni-Mn alloy plate subjected to the cold rolling treatment at room temperature in a box type resistance furnace at the temperature of 440 ℃, wherein the aging time is 73 h. The obtained cold-rolled Cu-Ni-Mn alloy plate after the aging treatment has the strength of 1398.9MPa, the self-corrosion potential of-0.126V and the self-corrosion current density of 4.07 multiplied by 10-3A/cm2The corrosion rate was 3.80mm/year, and the polarization resistance was 4.16X 102Ω·cm2。
Example 3
A preparation method of a high-strength and high-corrosion-resistance Cu-Ni-Mn alloy comprises the steps of preparing the Cu-Ni-Mn alloy by a vacuum induction melting method, preparing pure T2 copper, electrolytic nickel and electrolytic manganese according to a proportion of 20%, carrying out melting at 1150 ℃, keeping the temperature for 7min after furnace burden is completely melted, adding modifier boron powder and the like, heating and stirring for 18min, and then pouring by using a water-cooling copper mold to obtain a Cu-Ni-Mn alloy ingot.
Machining the Cu-Ni-Mn alloy subjected to vacuum induction melting into an ingot with the diameter D of 58mm and the length L of 300mm, wrapping a copper sheet with the thickness of 0.9mm, placing the copper sheet in a nitrogen heating furnace with the heating temperature of 950 ℃ for softening treatment, keeping the temperature for 90 +/-5 min, immediately placing the copper sheet in an extrusion cylinder preheated to 400 ℃ for hot extrusion treatment after the heat preservation is finished, controlling the extrusion force to be 3550KN, controlling the extrusion rate to be 29mm/s and the extrusion ratio to be 9:1, and finally obtaining the hot-extruded Cu-Ni-Mn alloy test bar with the diameter D of 20 mm.
Turning the Cu-Ni-Mn alloy test bar subjected to the hot extrusion treatment to 15mm, and then performing cold rolling treatment by using a vertical cold rolling mill at room temperature, wherein the cold rolling direction is performed along the hot extrusion axial direction, the final cold rolling thickness of the alloy is controlled to be 2mm in the cold rolling treatment process, and the deformation of each part of the alloy is ensured to be uniform and consistent by reciprocating twice in each pass in the deformation process.
And (3) carrying out aging treatment on the Cu-Ni-Mn alloy plate subjected to the cold rolling treatment at room temperature in a box type resistance furnace at the temperature of 425 ℃, wherein the aging time is 71 h. The surface of the alloy plate after aging treatment is polished by abrasive paper with the granularity of 280# to 1200#, the abrasive paper grinding mark of the next pass completely covers the abrasive paper grinding mark of the previous pass until the grinding is bright, and then the pulse of an electric pulse power supply is adjustedImpulse voltage and impulse frequency, controlling the root mean square current density to 9.80X 106A/m2The electric pulse treatment time is 150s, and air cooling is carried out after the treatment is finished, so as to obtain the high-strength high-corrosion-resistance Cu-Ni-Mn alloy, the strength of which is 1266.6MPa, the self-corrosion potential of which is-0.335V, and the self-corrosion current density of which is 5.76 multiplied by 10-5A/cm2The corrosion rate is 0.053mm/year, and the polarization resistance is 5.37X 104Ω·cm2。
Example 4
A preparation method of a high-strength high-corrosion-resistance Cu-Ni-Mn alloy comprises the steps of preparing the high-strength high-corrosion-resistance Cu-Ni-Mn alloy, preparing the Cu-Ni-Mn alloy by a vacuum induction melting method, preparing the Cu-Ni-Mn alloy by adopting T2 pure copper, electrolytic nickel and electrolytic manganese according to a proportion of 20%, carrying out melting at 1155 ℃, keeping the temperature for 9min after furnace burden is completely melted, adding modifier boron powder and the like, heating and stirring for 16min, and then pouring by using a water-cooling copper mold to obtain a Cu-Ni-Mn alloy cast ingot.
Machining a Cu-Ni-Mn alloy subjected to vacuum induction melting into an ingot with the diameter D of 59mm and the length L of 185mm, wrapping a copper sheet with the thickness of 0.6mm, placing the copper sheet in a nitrogen heating furnace with the heating temperature of 957 ℃ for softening, keeping the temperature for 93min, immediately placing the copper sheet in an extrusion cylinder preheated to 403 ℃ for hot extrusion treatment after the heat preservation is finished, controlling the extrusion force of 3520KN, wherein the extrusion rate is 23mm/s, and the extrusion ratio is 9:1, and finally obtaining the hot-extruded Cu-Ni-Mn alloy test bar with the diameter D of 20 mm.
Turning the Cu-Ni-Mn alloy test bar subjected to the hot extrusion treatment to 16mm, and then performing cold rolling treatment by using a vertical cold rolling mill at room temperature, wherein the cold rolling direction is performed along the hot extrusion axial direction, the final cold rolling thickness of the alloy is controlled to be about 5mm in the cold rolling treatment process, and the deformation of each part of the alloy is ensured to be uniform and consistent by reciprocating twice in each pass in the deformation process.
And (3) carrying out aging treatment on the Cu-Ni-Mn alloy plate subjected to the cold rolling treatment at room temperature in a box type resistance furnace at the temperature of 430 ℃, wherein the aging time is 73 h. The surface of the alloy plate after aging treatment is polished by abrasive paper with the granularity of 280# to 1200#, the abrasive paper grinding mark of the next pass completely covers the abrasive paper grinding mark of the previous pass until the grinding is bright, and then the pulse of an electric pulse power supply is adjustedImpulse voltage and impulse frequency, controlling the root mean square current density to be 1.00 multiplied by 107A/m2The electric pulse treatment time is 156s, and air cooling is carried out after the treatment is finished, so as to obtain the high-strength high-corrosion-resistance Cu-Ni-Mn alloy, the strength of which is 1266.1MPa, the self-corrosion potential of which is-0.296V, and the self-corrosion current density of which is 8.16 multiplied by 10-5A/cm2The corrosion rate is 0.076mm/year, and the polarization resistance is 4.12X 104Ω·cm2. As shown in FIG. 3, FIG. 3 is a photograph showing the structure of the high-strength and high-corrosion-resistance Cu-Ni-Mn alloy of the present example.
Example 5
A preparation method of a high-strength and high-corrosion-resistance Cu-Ni-Mn alloy adopts a vacuum induction melting method to prepare the Cu-Ni-Mn alloy, adopts T2 pure copper, electrolytic nickel and electrolytic manganese which are proportioned according to a proportion of 20%, the melting temperature is carried out at 1138 ℃, the furnace burden is completely melted, heat is preserved for 8min, modifier boron powder and the like are added, the mixture is heated and stirred for 18min, and then a water-cooling copper mold is used for pouring, so that a Cu-Ni-Mn alloy cast ingot is obtained.
Machining the Cu-Ni-Mn alloy subjected to vacuum induction melting into an ingot with the diameter D of 61mm and the length L of 230mm, wrapping a copper sheet with the thickness of 0.8mm, placing the copper sheet in a nitrogen heating furnace with the heating temperature of 946 ℃ for softening treatment, keeping the temperature for 86min, immediately placing the copper sheet in an extrusion cylinder preheated to 399 ℃ for hot extrusion treatment after the heat preservation is finished, controlling the extrusion force of 3565KN, wherein the extrusion rate is 20-32 mm/s, and the extrusion ratio is 9:1, and finally obtaining the hot-extruded Cu-Ni-Mn alloy test bar with the diameter D of 20 mm.
Turning the Cu-Ni-Mn alloy test bar subjected to the hot extrusion treatment to 12mm, and then performing cold rolling treatment by using a vertical cold rolling mill at room temperature, wherein the cold rolling direction is performed along the hot extrusion axial direction, the final cold rolling thickness of the alloy is controlled to be about 4mm in the cold rolling treatment process, and the deformation of each part of the alloy is ensured to be uniform and consistent by reciprocating twice in each pass in the deformation process.
And (3) carrying out aging treatment on the Cu-Ni-Mn alloy plate subjected to the cold rolling treatment at room temperature in a box type resistance furnace at the temperature of 430 ℃, wherein the aging time is 69 h. The surface of the alloy plate after aging treatment is polished by abrasive paper with the granularity of 280# to 1200#, and the grinding mark of the next pass completely covers the grinding mark of the abrasive paper of the previous pass and is straightPolishing until the color is bright, and then controlling the root mean square current density to be 1.16 multiplied by 10 by adjusting the pulse voltage and the pulse frequency of an electric pulse power supply7A/m2The electric pulse treatment time is 146s, air cooling is carried out after the treatment is finished, and the high-strength and high-corrosion-resistance Cu-Ni-Mn alloy with the strength of 629.2MPa, the self-corrosion potential of-0.144V and the self-corrosion current density of 2.21 multiplied by 10 is obtained-3A/cm2The corrosion rate is 2.051mm/year, and the polarization resistance is 1.99 multiplied by 103Ω·cm2。
FIG. 2 is a stress-strain curve of the Cu-Ni-Mn alloy of examples 1 to 5, and it can be seen that the strength of the Cu-Ni-Mn alloy gradually decreases and the plasticity gradually increases as the pulse current density increases.
FIG. 1 is a Tafel plot of the Cu-Ni-Mn alloys of examples 1-5, and it can be seen that the corrosion resistance of the Cu-Ni-Mn alloy increases first and then decreases as the pulse current density increases, when the current density ranges from 9.80X 106A/m2～1.00×107A/m2And the corrosion resistance is far higher than that of the Cu-Ni-Mn alloy subjected to hot extrusion and cold rolling treatment and hot extrusion, cold rolling and aging treatment.
FIG. 4 is a Nyquist plot of Cu-Ni-Mn alloys of examples 1-5 after fitting, and it can be seen that the impedance values of Cu-Ni-Mn alloys increase and then decrease as the pulse current density increases, when the current density ranges from 9.80X 106A/m2～1.00×107A/m2When the alloy is used, the impedance value is higher than that of the Cu-Ni-Mn alloy subjected to hot extrusion and cold rolling treatment and hot extrusion, cold rolling and aging treatment.
The preparation method of the high-strength high-corrosion resistance Cu-Ni-Mn alloy improves the micro segregation in the as-cast structure of the alloy, and leads the alloy to generate dynamic recovery recrystallization, so that the structure is changed from a coarse dendritic crystal with poor comprehensive performance to a fine isometric crystal with good comprehensive performance; meanwhile, the strength of the alloy is greatly improved, the resistivity and the internal energy storage of the alloy are obviously improved, good conditions are provided for subsequent electric pulse treatment, the influence of grain boundary preferential precipitation on the mechanical property and the corrosion resistance of the alloy is favorably reduced, the strength of the alloy is greatly improved, the corrosion tendency of the alloy is reduced, and the corrosion resistance of the alloy is improved while the high strength of the alloy is ensured.
Claims (6)
1. A preparation method of a high-strength high-corrosion-resistance Cu-Ni-Mn alloy is characterized by comprising the following steps:
step 1: preparing a Cu-Ni-Mn alloy ingot by a vacuum induction melting method;
step 2: carrying out hot extrusion treatment on the Cu-Ni-Mn alloy cast ingot in the step 1, and then carrying out cold rolling treatment on the hot extruded Cu-Ni-Mn alloy at room temperature;
and step 3: and (3) performing electric pulse treatment on the alloy subjected to cold rolling treatment in the step (2) to obtain the high-strength and high-corrosion-resistance Cu-Ni-Mn alloy.
2. The method for preparing the high-strength high-corrosion-resistance Cu-Ni-Mn alloy according to claim 1, characterized in that in the step 1, the specific process is as follows: adopting T2 pure copper, adding 20% of electrolytic nickel and 20% of electrolytic manganese, carrying out smelting at 1135-1165 ℃, keeping the temperature for 5-10 min after furnace burden is completely melted, adding a modifier, heating and stirring for 15-20 min, and then pouring by using a water-cooling copper mold to obtain a Cu-Ni-Mn alloy cast ingot.
3. The method of claim 2, wherein in step 1, the modifying agent is boron powder.
4. The method for preparing a high-strength high-corrosion-resistance Cu-Ni-Mn alloy according to claim 1, wherein in the step 2, the hot extrusion treatment comprises the following specific steps: wrapping a copper sheet with the thickness of 0.5-1 mm on a Cu-Ni-Mn alloy ingot, placing the Cu-Ni-Mn alloy ingot in a nitrogen heating furnace with the heating temperature of 940-960 ℃ for softening treatment, keeping the temperature for 85-95 min, placing the Cu-Ni-Mn alloy ingot in an extrusion cylinder preheated to 395-405 ℃ for hot extrusion treatment after the heat preservation is finished, controlling the extrusion force to be not lower than 3500KN, the extrusion rate to be 20-32 mm/s and the extrusion ratio to be 9:1, and then obtaining the Cu-Ni-Mn alloy test bar.
5. The method for preparing the high-strength high-corrosion-resistance Cu-Ni-Mn alloy according to claim 4, wherein the step 2 is a cold rolling treatment at room temperature, and the specific process comprises the following steps: turning the Cu-Ni-Mn alloy test bar subjected to the hot extrusion treatment, and then performing cold rolling treatment on the alloy test bar by using a vertical cold rolling mill at room temperature, wherein the cold rolling direction is performed along the axial direction of the hot extrusion, and the deformation of each part of the alloy is ensured to be uniform and consistent by reciprocating twice in each pass in the deformation process.
6. The method for preparing the high-strength high-corrosion-resistance Cu-Ni-Mn alloy according to claim 1, wherein in the step 3, the specific process of the electric pulse treatment is as follows: carrying out aging treatment on the Cu-Ni-Mn alloy plate subjected to cold rolling treatment at room temperature in a resistance furnace at the temperature of 400-450 ℃, wherein the aging time is 65-75 h, then polishing the plate to be bright by using sand paper, and then controlling the root mean square current density to be 9.80 multiplied by 10 by adjusting the pulse voltage and the pulse frequency of an electric pulse power supply6A/m2～1.24×107A/m2And (3) carrying out electric pulse treatment for 140-160 s, and carrying out air cooling after the treatment is finished to obtain the high-strength and high-corrosion-resistance Cu-Ni-Mn alloy.
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