CN115627378A - Preparation method of Cu-Al-Zn alloy material - Google Patents
Preparation method of Cu-Al-Zn alloy material Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 40
- 229910017777 Cu—Al—Zn Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 43
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005096 rolling process Methods 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000012535 impurity Substances 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 238000003723 Smelting Methods 0.000 claims abstract description 8
- 238000005303 weighing Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 29
- 230000008569 process Effects 0.000 claims description 16
- 238000005098 hot rolling Methods 0.000 claims description 11
- 238000005097 cold rolling Methods 0.000 claims description 10
- 238000007709 nanocrystallization Methods 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims 1
- 239000010949 copper Substances 0.000 abstract description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052802 copper Inorganic materials 0.000 abstract description 16
- 239000013078 crystal Substances 0.000 description 14
- 238000012545 processing Methods 0.000 description 9
- 229910000838 Al alloy Inorganic materials 0.000 description 5
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical group [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000002707 nanocrystalline material Substances 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- -1 copper-aluminum-zinc Chemical compound 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- C22C9/00—Alloys based on copper
- C22C9/01—Alloys based on copper with aluminium 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
-
- 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
- C22C9/04—Alloys based on copper with zinc as the next major constituent
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Metal Rolling (AREA)
Abstract
The invention discloses a preparation method of a Cu-Al-Zn alloy material, and belongs to the technical field of preparation of copper alloy materials. Weighing raw materials according to the weight percentage of 89-91 wt%, al4.5-5.5 wt% and Zn4.5-5.5 wt%, adding the raw materials into a furnace for smelting, and preserving heat for a period of time to obtain an original copper alloy material; removing impurities on the surface of the original copper alloy material, and rolling the original material, wherein the deformation of each pass is controlled in each rolling; removing impurities left on the surface of the plate after rolling, putting the plate into a surface nano device, introducing liquid nitrogen for treatment while treating, and obtaining the high-performance copper alloy after the treatment is finished. Compared with the traditional pure copper, the high-performance copper alloy material prepared by the invention has yield strength of more than 260MPa, tensile strength of more than 400MPa and uniform elongation of more than 50%, and has excellent formability and durability when being applied to a structural member.
Description
Technical Field
The invention relates to a preparation method of a Cu-Al-Zn alloy material, belonging to the technical field of preparation of copper alloy materials.
Background
Copper and copper alloy are still the basic materials widely demanded in various industries of global economy, are second only to iron/steel and aluminum in production and consumption, and are located in the third place; they are widely used in the mechanical, marine, automotive, chemical and electronic industries because of their excellent electrical and thermal conductivity, corrosion resistance, and easy weldability; the common copper alloy is copper-aluminum alloy, the strength and hardness of the copper alloy can be improved by adding aluminum, but the plasticity of the copper alloy is correspondingly reduced; and the addition of a proper amount of zinc element not only has the solid solution strengthening effect, but also can improve the plasticity of the copper-aluminum alloy to a certain extent. Therefore, the research on the mechanical properties of copper-aluminum-zinc alloy has received much attention in recent years. Over the past decades, nanocrystalline and ultrafine grained metal materials have gained widespread attention due to their high strength; one of the most popular methods for preparing nanocrystalline materials is the macroplastic deformation technique.
Large plastic deformation techniques can be achieved by mechanically applying extensive hydrostatic pressure and very high strain to bulk metallic materials; this technique allows the grains of the material to be significantly refined and thus the strength of the material to be increased. Typical large shaping techniques include equal channel angular extrusion, high pressure torsion, dynamic plastic deformation, and cumulative pack rolling. However, the ductility of high strength nanocrystalline materials prepared by such methods is generally low, which greatly limits their applications. With the progress of science and technology and the development of society, people have higher and higher requirements on copper materials. Besides excellent electrical and thermal conductivity, the gradient structure material also needs to have good mechanical properties, so that the gradient structure material is widely concerned and applied due to the excellent properties.
Disclosure of Invention
The invention aims to provide a preparation method of a Cu-Al-Zn alloy material, aiming at providing a Cu-Al-Zn alloy material combining high strength and high plasticity, wherein the strength and the ductility of the copper alloy material are improved compared with those of a traditional pure copper material, and the preparation method specifically comprises the following steps:
(1) Weighing the raw materials according to the weight percentage of 89-91 wt percent, 4.5-5.5 wt percent and Zn4.5-5.5 wt percent, adding the raw materials into a furnace for smelting, and preserving heat for a period of time to obtain the original copper alloy material.
(2) Removing impurities on the surface of the original copper alloy material, and rolling the original material, wherein the deformation of each pass is controlled in each rolling.
(3) Removing impurities left on the surface of the plate after rolling, putting the plate into a surface nanocrystallization device for treatment, continuously introducing liquid nitrogen in the surface nanocrystallization process, obtaining the high-performance copper alloy after the treatment is finished, and introducing a series of defects in the surface nanocrystallization process to change the microstructure inside the material, so that the mechanical property of the material is improved. The liquid nitrogen can remove impurity gas in the working cavity, create an inert gas environment, inhibit dynamic recovery of dislocation, promote formation of deformation twin crystals and form a nano gradient structure, the nano gradient structure formed in the low-temperature environment is not only a gradient of crystal grain size, but also a certain amount of deformation twin crystal tissues are arranged in each crystal grain, so that a gradient structure is formed on a substructure, and the two gradient structures jointly influence the mechanical property of the material.
Preferably, the smelting in the step (1) of the invention specifically comprises: heating the raw materials to 1200-1250 ℃ within 120-180 min, and preserving heat for at least 3h.
Preferably, the method for removing the surface impurities is to polish the surface of the material smoothly by using an angle grinder and sand paper.
Preferably, the rolling in the step (3) of the invention comprises hot rolling and cold rolling, wherein the deformation of the hot rolling is controlled to be 8-12% per time, the deformation of the cold rolling is controlled to be 4~6%, and the thickness of the obtained plate is 1-5 mm.
Preferably, 208 stainless steel balls with the diameter of 6mm are arranged in a working cavity in the surface nano device in the step (5), the treatment time is 8min, and the vibration frequency is about 50Hz; the area of the bottom of the working cavity of the surface nano device is about 36000mm 2 The surface area occupied by 208 steel balls is about 24000mm 2 At this ratio, 208 steel balls in the working chamber can uniformly impact the surface of the sample.
The aluminum element added in the method can play a role in solid solution strengthening, can improve the hardness, the strength, the wear resistance and the corrosion resistance, but can reduce the plasticity.
Zn is added into the copper-aluminum alloy in the method and can be dissolved in the copper-aluminum alloy in a solid solution mode, so that the solid solution strengthening effect is achieved, and the plasticity of the copper-aluminum alloy can be improved.
The high-performance copper alloy is most likely to cause surface peeling in the subsequent processing process, particularly the hot rolling process, and is easy to influence the subsequent treatment, and the phenomenon can be effectively improved by adding aluminum and Zn.
The Cu-Al-Zn alloy material disclosed by the invention is high in strength, good in plasticity, corrosion resistance and wear resistance, can be applied to the propeller and the structure of a ship, and can improve the strength, plasticity and corrosion resistance of the ship structural member and prolong the service life of the ship propeller.
Compared with the prior art, the invention has at least the following advantages:
(1) Compared with the traditional pure copper, the mechanical property of the copper is improved, and the good combination of strength and plasticity is mainly reflected; the yield strength of the high-performance copper alloy material prepared by the embodiment of the invention is more than 260MPa, the tensile strength is more than 400MPa, the uniform elongation is more than 50%, and the high-performance copper alloy material has excellent formability and durability when being applied to a structural member.
(2) The surface hardness of the high-performance copper alloy material is improved after treatment, and compared with the traditional pure copper material, the high-performance copper alloy material has stronger deformation resistance.
(3) The method adopts the method of introducing liquid nitrogen during the surface nanocrystallization process, and the introduced liquid nitrogen can not only discharge the air in the working cavity to prevent the reaction of the sample and the air, but also reduce the working temperature during the surface nanocrystallization process, inhibit the dynamic recovery of dislocation and promote the generation of deformation twin crystals, thereby further influencing the microstructure inside the material to form the material with more excellent gradient structure.
Drawings
FIG. 1 is a schematic view of a surface-nanocrystallization apparatus used in example 1 of the present invention;
FIG. 2 is a drawing graph of a high-performance copper alloy according to example 1 of the present invention and a conventional pure copper material;
FIG. 3 is a gold phase diagram of a high performance copper alloy of example 1 of the present invention;
FIG. 4 is a hardness profile from the surface to the core of the high-performance copper alloy according to example 1 of the present invention and a conventional pure copper material.
Detailed Description
The invention will be described in more detail with reference to the following figures and examples, but the scope of the invention is not limited thereto.
Example 1
A preparation method of a Cu-Al-Zn alloy material, which controls the types and contents of all components to play a role in synergy among the components, thereby endowing high-performance Cu-Al-Zn alloy fittings with excellent plasticity and higher strength, comprises the following steps:
(1) Weighing the raw materials according to the weight percentage of 90wt% of Cu, 4.5wt% of Al and 5.5 wt% of Zns, adding the raw materials into a furnace for smelting, and preserving heat for a period of time to obtain the original copper alloy material.
(2) Removing impurities on the surface of the original copper alloy material, and rolling the original material, wherein the deformation of each pass is controlled in each rolling; heating the raw materials to 1230 ℃ within 150min, and preserving the heat for at least 3h. The rolling comprises hot rolling and cold rolling, wherein the deformation of each time of the hot rolling is controlled at 8%, the deformation of each time of the cold rolling is controlled at 4%, and the thickness of the obtained plate is 5mm.
(3) The surface of the material is polished by an angle grinder and abrasive paper to remove impurities left on the surface of the plate after rolling, the plate is placed into a surface nano device for processing, high-performance copper alloy is obtained after the processing, a series of defects are introduced in the surface nano process to change the microstructure inside the material, and thus the mechanical property of the material is improved. 208 stainless steel balls with the diameter of 6mm are arranged in a working cavity in the surface nano device, liquid nitrogen is continuously introduced in the treatment process, the treatment time is 8min, and the vibration frequency is about 50Hz.
When mechanical testing is carried out, firstly, a plate is cut into a dog-bone-shaped tensile sample by a wire cutting machine, the position of the wire cutting position is polished to be smooth before stretching, particularly, the surface roughness of the arc transition position must be small, otherwise, a sample is not easy to break in the middle in the stretching process.
The tensile testing machine is adopted to test the strength of the material, the dog bone-shaped tensile sample with the sample size of 4.76 x 3.89 has the yield strength of 278.88MPa, the tensile strength of 419MPa, the uniform elongation of 51.20 percent, the strain rate of 0.45mm/min, the yield strength improved by 2.5 times compared with pure copper, the tensile strength improved by 1.5 times, the uniform elongation improved by 25 percent, and the comprehensive mechanical property greatly improved compared with the pure copper.
FIG. 3 is a gold phase diagram of a high performance copper alloy of example 1 of the present invention; it can be seen from the figure that a large number of deformed twin crystals exist inside the crystal grains, and the dislocation traces are relatively few, which is a phenomenon caused by the low-temperature environment of liquid nitrogen.
FIG. 4 is a graph showing hardness curves of the high-performance copper alloy of example 1 of the present invention and a conventional pure copper material from the surface to the core; as can be seen from the figure, the hardness of the pure copper does not change with the increase of the depth, and the hardness of the high-performance copper alloy material also decreases with the increase of the depth (0-600 micrometers), which indicates that the high-performance copper alloy is a gradient structural material.
Example 2
A preparation method of a Cu-Al-Zn alloy material, which controls the types and contents of all components to play a role in synergy among the components, thereby endowing high-performance Cu-Al-Zn alloy fittings with excellent plasticity and higher strength, comprises the following steps:
(1) Weighing the raw materials according to the weight percentage of 89wt% of Cu, 5.5 wt% of Al and 5.5 wt% of Zns, adding the raw materials into a furnace for smelting, and preserving heat for a period of time to obtain the original copper alloy material.
(2) Removing impurities on the surface of the original copper alloy material, and rolling the original material, wherein the deformation of each pass is controlled in each rolling; the raw materials are heated to 1250 ℃ within 180min, and the temperature is kept for at least 3h. The rolling comprises hot rolling and cold rolling, the deformation of each time of the hot rolling is controlled at 12%, the deformation of each time of the cold rolling is controlled at 6%, and the thickness of the obtained plate is 1mm.
(3) The surface of the material is polished by an angle grinder and abrasive paper to remove impurities left on the surface of the plate after rolling, the plate is placed into a surface nano device for processing, high-performance copper alloy is obtained after the processing, a series of defects are introduced in the surface nano process to cause the change of the microstructure inside the material, and thus the mechanical property of the material is improved. 208 stainless steel balls with the diameter of 6mm are arranged in a working cavity in the surface nano device, liquid nitrogen is continuously introduced in the treatment process, the treatment time is 8min, and the vibration frequency is about 50Hz.
The tensile testing machine is adopted to test the strength of the material, the dog bone-shaped tensile sample with the sample size of 4.76 x 3.89 has the yield strength of 278.88MPa, the tensile strength of 419MPa, the uniform elongation of 51.2 percent, the used strain rate of 0.45mm/min, the yield strength improved by about 2.5 times compared with pure copper, the tensile strength improved by about 1.5 times, the uniform elongation improved by about 25 percent and the comprehensive mechanical property greatly improved compared with pure copper.
Example 3
A preparation method of a Cu-Al-Zn alloy material, which controls the types and contents of all components to play a role in synergy among the components, thereby endowing high-performance Cu-Al-Zn alloy fittings with excellent plasticity and higher strength, comprises the following steps:
(1) Weighing the raw materials according to the weight percentage of 91 wt% of Cu, 4.5wt% of Al4, and 4.5wt% of Zns, adding the raw materials into a furnace for smelting, and preserving heat for a period of time to obtain the original copper alloy material.
(2) Removing impurities on the surface of the original copper alloy material, and rolling the original material, wherein the deformation of each pass is controlled in each rolling; heating the raw materials to 1200 ℃ within 120min, and keeping the temperature for at least 3h. The rolling comprises hot rolling and cold rolling, wherein the deformation of each arriving time of the hot rolling is controlled at 10%, the deformation of each arriving time of the cold rolling is controlled at 5%, and the thickness of the obtained plate is 3mm.
(3) The surface of the material is polished by an angle grinder and abrasive paper to remove impurities left on the surface of the plate after rolling, the plate is placed into a surface nano device for processing, high-performance copper alloy is obtained after the processing, a series of defects are introduced in the surface nano process to change the microstructure inside the material, and thus the mechanical property of the material is improved. 208 stainless steel balls with the diameter of 6mm are arranged in a working cavity in the surface nano device, liquid nitrogen is continuously introduced in the treatment process, the treatment time is 8min, and the vibration frequency is about 50Hz.
The tensile testing machine is adopted to test the strength of the material, the dog bone-shaped tensile sample with the sample size of 4.76 x 3.89 has the yield strength of 278.88MPa, the tensile strength of 419MPa, the uniform elongation of 51.20 percent, the strain rate of 0.45mm/min, the yield strength improved by 2.5 times compared with pure copper, the tensile strength improved by 1.5 times, the uniform elongation improved by 25 percent, and the comprehensive mechanical property greatly improved compared with the pure copper.
In the processing process, 208 small steel balls in a working cavity in the surface nanocrystallization device bombard the surface of a plate at the frequency of 50Hz under the action of a centrifugal machine, in the bombardment process, a large amount of dislocation is firstly introduced into the surface of the material to refine crystal grains on the surface of the plate, then the dynamic recovery of the dislocation is inhibited in a low-temperature environment with liquid nitrogen introduced, the crystal grains are further refined, a certain amount of deformed twin crystals are easily generated in the temperature environment of the liquid nitrogen, the generation of the deformed twin crystals can block the movement of the dislocation in the crystal grains to further improve the mechanical property of the material, after the surface nanocrystallization processing is finished, a surface of the material is formed into a nano crystal, a secondary surface of the material is an ultrafine crystal, a core of the material is a coarse crystal gradient structure, and the strength and the plasticity of the gradient material can be further improved due to the effect of HDI stress. And removing the sample from the device after the treatment is finished, and cleaning the surface to obtain the high-performance copper alloy material for the small-sized structural member.
Claims (5)
1. The preparation method of the Cu-Al-Zn alloy material is characterized by comprising the following steps:
(1) Weighing the raw materials according to the weight percentage of 89-91 wt percent by weight, 4.5-5.5 wt percent by weight and 4.5-5.5 wt percent by weight, adding the raw materials into a furnace for smelting, and preserving heat for a period of time to obtain an original copper alloy material;
(2) Removing impurities on the surface of the original copper alloy material, and rolling the original material, wherein the deformation of each pass is controlled in each rolling;
(3) Removing impurities left on the surface of the plate after rolling, putting the plate into a surface nanocrystallization device for treatment, continuously introducing liquid nitrogen in the surface nanocrystallization process, and obtaining the high-performance copper alloy after the treatment is finished.
2. The method for producing a Cu-Al-Zn alloy material according to claim 1, wherein: the smelting in the step (1) is specifically as follows: heating the raw materials to 1200-1250 ℃ within 120-180 min, and preserving heat for at least 3h.
3. The method for producing a Cu-Al-Zn alloy material according to claim 1, wherein: the method for removing the surface impurities specifically comprises the step of polishing the surface of the material to be smooth by using an angle grinder and abrasive paper.
4. The method for producing a Cu-Al-Zn alloy material according to claim 1, wherein: the rolling in the step (3) comprises hot rolling and cold rolling, wherein the deformation of the hot rolling is controlled to be 8 to 12 percent each time, and the deformation of the cold rolling is controlled to be 4~6 percent each time.
5. The method for preparing a Cu-Al-Zn alloy material according to claim 1, wherein: and (53) arranging 208 stainless steel balls with the diameter of 6mm in a working cavity in the surface nano device, and continuously introducing liquid nitrogen in the treatment process, wherein the treatment time is 8min, and the vibration frequency is about 50Hz.
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- 2022-10-19 CN CN202211280136.3A patent/CN115627378A/en active Pending
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Application publication date: 20230120 |