CN118086718B - Copper alloy wire, preparation method and application thereof - Google Patents
Copper alloy wire, preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000956 alloy Substances 0.000 claims abstract description 58
- 230000007797 corrosion Effects 0.000 claims abstract description 43
- 238000005260 corrosion Methods 0.000 claims abstract description 43
- 239000010949 copper Substances 0.000 claims abstract description 24
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 229910045601 alloy Inorganic materials 0.000 claims description 52
- 238000011282 treatment Methods 0.000 claims description 44
- 239000011701 zinc Substances 0.000 claims description 37
- 238000009749 continuous casting Methods 0.000 claims description 29
- 238000002844 melting Methods 0.000 claims description 26
- 230000008018 melting Effects 0.000 claims description 26
- 238000000137 annealing Methods 0.000 claims description 23
- 238000010622 cold drawing Methods 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 17
- 238000005266 casting Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 229910052718 tin Inorganic materials 0.000 claims description 10
- 238000005096 rolling process Methods 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 238000003723 Smelting Methods 0.000 claims description 8
- 238000005275 alloying Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 206010040844 Skin exfoliation Diseases 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 230000005672 electromagnetic field Effects 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 238000009360 aquaculture Methods 0.000 claims description 4
- 244000144974 aquaculture Species 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 27
- 230000008569 process Effects 0.000 abstract description 21
- 238000005452 bending Methods 0.000 abstract description 18
- 229910052759 nickel Inorganic materials 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012545 processing Methods 0.000 description 11
- 239000013078 crystal Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000013535 sea water Substances 0.000 description 5
- 238000009313 farming Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
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- 238000001953 recrystallisation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 2
- 229910000905 alloy phase Inorganic materials 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000009991 scouring Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 208000002720 Malnutrition Diseases 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- XTYUEDCPRIMJNG-UHFFFAOYSA-N copper zirconium Chemical compound [Cu].[Zr] XTYUEDCPRIMJNG-UHFFFAOYSA-N 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/04—Alloys based on copper with zinc as the next major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
- B22D11/004—Copper 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
- C22C1/02—Making non-ferrous alloys by melting
-
- 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)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Conductive Materials (AREA)
Abstract
The invention provides a copper alloy wire, a preparation method and application thereof. The copper alloy wire comprises the following components in percentage by weight: 65-85 wt% of Cu, 0.5-2 wt% of Sn, 0.2-2.0 wt% of Al, 0.05-0.5 wt% of Ti, 0.05-1.5 wt% of Si, and the balance of Zn and unavoidable impurity elements, wherein the components of the copper alloy wire do not comprise Ni, fe, mg, B, zr, cr and Co; in the copper alloy wire, 20< [ Zn ] eq <38. Aiming at the problems that the existing copper alloy material relates to a plurality of element types and has complex process, the copper alloy with specific component content is provided, so that the metal elements in the copper alloy material act synergistically, the grain size is optimized, and the copper alloy wire with low corrosion rate and strong bending resistance is obtained.
Description
Technical Field
The invention relates to the technical field of nonferrous metal processing, in particular to a copper alloy wire, a preparation method and application thereof.
Background
Conventional marine farming materials are typically made of nylon or other chemical fiber materials. However, during marine farming these materials are prone to microorganism growth and cause fouling of large amounts of marine organisms, which hampers the mobility of the body of aquaculture water and thus causes diseases and malnutrition problems for the farming. In contrast, copper alloy is an ideal material for current and future aquaculture net cages because copper ions can be released and the breeding and fouling of microorganisms and marine organisms can be effectively prevented.
The copper alloy is mainly used for manufacturing the netting and binding the netting and the frame as the cultivation material. However, the current copper alloy materials have problems in the strapping and connecting process, including intolerance to repeated bending, susceptibility to breakage, uneven corrosion, and the like. These problems lead to accelerated corrosion and reduced material life. To solve these problems, it is necessary to modify the copper alloy material to improve durability and stability thereof, thereby better satisfying the demands of marine farming.
In order to solve the above problems, many studies have been made by the expert in the art. Patent CN 100543162C proposes a series of alloys and a net cage structure thereof from the aspects of dezincification corrosion, non-beta phase proportion and grain refinement, as, sb, mg and P are added to refine cast grains, so As to inhibit dezincification corrosion; patent CN103403201a improves ductility and strength by adding a large amount of Ni, mn elements, but increases alloy cost; wherein the corresponding product is not consumed. However, the above-mentioned several prior arts are added with various elements, in which As, sb, etc. harmful to the environment are not lacking, which not only makes the processing technique more complex, but also is unfavorable for green development in the field; in addition, the added alloying elements also lead to a reduction in the repeated bending properties of the finished alloy wire.
Based on the above, how to provide a copper alloy wire with simple formula, easy processing, corrosion resistance and good repeated bending performance, which can be widely used in the field of marine culture as a net cage, net connection and binding material, and simultaneously avoid the defects of high cost, difficult processing and the like caused by more element types, is a technical problem to be solved in the field.
Disclosure of Invention
The invention mainly aims to provide a copper alloy wire, a preparation method and application thereof, and aims to solve the problems that the copper alloy wire in the prior art is complex in formula, various in element types, and poor in corrosion resistance and repeated bending performance.
In order to achieve the above object, according to one aspect of the present invention, there is provided a copper alloy wire, characterized in that the copper alloy wire comprises, in weight percent: 65 to 85 weight percent of Cu, 0.5 to 2 weight percent of Sn, 0.2 to 2.0 weight percent of Al, 0.05 to 0.5 weight percent of Ti, 0.05 to 1.5 weight percent of Si, and the balance of Zn and unavoidable impurity elements, wherein the components of the copper alloy wire do not comprise Ni, fe, mg, B, zr, cr and Co; in the copper alloy wire, 20< [ Zn ] eq. <38.
Further, the copper alloy wire comprises the following components in percentage by weight: 68 to 75 weight percent of Cu, 0.5 to 1.2 weight percent of Sn, 0.8 to 1.5 weight percent of Al, 0.1 to 0.3 weight percent of Ti, 0.2 to 0.8 weight percent of Si, and the balance of Zn and unavoidable impurity elements, wherein the components of the copper alloy wire do not comprise Ni, fe, mg, B, zr, cr and Co; in the copper alloy wire, 25< [ Zn ] eq. <36.
Further, the copper alloy wire comprises the following components in percentage by weight: 1.
Further, the grain size of the copper alloy wire is 30-80 μm.
The invention also provides a preparation method of the copper alloy wire, which comprises the following steps: step S1, melting and alloying: raw materials are put into a smelting device to be melted, and copper alloy melt is obtained; step S2, electromagnetic horizontal continuous casting: carrying out electromagnetic horizontal continuous casting on the copper alloy melt to obtain a copper alloy casting rod, wherein the temperature of electromagnetic horizontal continuous casting is 1100-1150 ℃; the electromagnetic horizontal continuous casting is carried out in a continuous casting crystallizer, the alternating electromagnetic field current of the continuous casting crystallizer is 20-100A, and the frequency is 20-50 Hz; step S3, deformation and heat treatment: and sequentially carrying out rolling treatment, first annealing treatment, first cold drawing treatment, surface peeling treatment, second annealing treatment and second cold drawing treatment on the copper alloy cast rod to obtain the copper alloy wire.
Further, the diameter of the copper alloy casting rod in the step S2 is 15-20 mm, and the grain size is 200-500 mu m.
Further, in step S3, the deformation amount of the rolling treatment is 75 to 95%; the deformation of the first cold drawing treatment is 50-70%; the deformation amount of the second cold drawing treatment is 25-40%.
Further, in the step S3, the temperature of the first annealing treatment is 550-650 ℃, and the heat preservation time is 2-6 hours, so as to obtain a first annealed wire; the grain size of the first annealed wire is 100-120 mu m; the temperature of the second annealing treatment is 500-650 ℃, and the heat preservation time is 2-6 hours, so as to obtain a second annealing wire; the grain size of the second annealed wire is 30-80 μm.
Further, the step of melting and alloying in step S1 further includes: s1-1, loading copper into a smelting device for first melting to obtain a first melt; s1-2, adding silicon into the first melt, and performing second melting to obtain a second melt; s1-3, cooling the second melt to 1100-1150 ℃, sequentially adding tin, aluminum, zinc and copper-titanium intermediate alloy into the second melt, and performing third melting to obtain a copper alloy melt; the first and second melts are each independently at a temperature of 1200 to 1240 ℃ and the third melt is at a temperature of 1100 to 1150 ℃.
In a further aspect, the invention provides the application of the copper alloy wire in the field of marine culture, wherein the copper alloy wire is used as a corrosion-resistant marine culture net cage material, a net connecting and binding wire belt material.
By applying the technical scheme of the invention, aiming at the problems that the existing copper alloy material relates to a plurality of element types and has complex process, the copper alloy with specific component content is provided, so that the metal elements in the copper alloy material act synergistically, the grain size is optimized, the copper alloy wire with low corrosion rate and strong bending resistance is obtained, and the copper alloy wire can be suitable for net cage, net connection and bundling of different sea areas. And the method is beneficial to reducing the process complexity while ensuring good application performance of the copper alloy wire due to simple element types.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The present application will be described in detail with reference to examples.
As described in the background art, the prior art has the problems of complex formula of copper alloy wires, multiple types of elements, poor corrosion resistance and poor repeated bending performance. In order to solve the technical problems, the invention provides a copper alloy wire, which comprises the following components in percentage by weight: 65 to 85 weight percent of Cu, 0.5 to 2 weight percent of Sn, 0.2 to 2.0 weight percent of Al, 0.05 to 0.5 weight percent of Ti, 0.05 to 1.5 weight percent of Si, and the balance of Zn and unavoidable impurity elements, wherein the components of the copper alloy wire do not comprise Ni, fe, mg, B, zr, cr and Co; in the copper alloy wire, 20< [ Zn ] eq. <38.
The invention reasonably selects the component types of the copper alloy, optimizes the use amount of each element through component design, and thus realizes the improvement of corrosion resistance and bending resistance through a simple alloy formula in cooperation with the cooperation among the elements. Specifically, in the alloy components, the Sn content is controlled to be 0.5-2 wt% so as to exert the corrosion resistance of the alloy; the Al content is controlled to be 0.2 to 2.0 weight percent so as to form an oxide film by utilizing the ionization trend of the Al, thereby improving the corrosion resistance of the copper alloy where the Al is positioned; the Ti content is controlled to be 0.05 to 0.5 weight percent, so that the micro grain size is better regulated and controlled, the plasticity is enhanced, and the performance is optimized; the content of Si is controlled to be 0.05-1.5 wt percent, so that the alloy strength is effectively improved, and the seawater scouring resistance is improved. The above elements are mutually matched while playing respective roles, and the alloy ingredient formula preferred in the invention is formed, so that the improvement of the corrosion resistance and bending resistance mechanical property of the copper alloy wire can be realized by a simpler composition. In addition, in the copper alloy wire provided by the invention, 20< [ Zn ] eq. <38, wherein [ Zn ] eq. is virtual zinc equivalent, and the calculation formula of the copper alloy wire is as follows:
[ Zn ] eq. =100 ([ Zn ] + [ M ])/([ Zn ] + [ M ] + [ Cu ]), [ M ] =2 ] [ Sn ] +6 [ Al ] -10 [ Si ]; [ Zn ] is the actual content of Zn element, [ Cu ] is the actual content of Cu element, [ Sn ] is the actual content of Sn element, [ Al ] is the actual content of Al element, [ Si ] is the actual content of Si element.
The invention realizes that the metallographic structure is single alpha phase by controlling the virtual zinc equivalent [ Zn ] eq. of the copper alloy wire to be 20-38, and inhibits the generation of other phase structures, thereby obviously improving the corrosion resistance of the obtained copper alloy wire and prolonging the service life thereof.
In particular, regarding the copper alloy compositions of Ni, fe, mg, B, zr, cr and Co, which are commonly used, they are not incorporated into the copper alloy wire compositions provided by the present invention, specifically:
Ni forms a compound with Al, ti and Si elements in the alloy, forms a single-phase structure with the alloy designed by the invention, and is deviated from an easy-to-process alloy phase, and the formed second phase reduces corrosion resistance;
the solid solubility of Fe element in copper is small, and a second phase which is rich in iron and separated out is easy to form at room temperature, so that the corrosion performance of the alloy is reduced, and the service life of the alloy in seawater is prolonged;
the Mg element and the Si element form a metal compound, the B element and the Ti element form a metal compound, and the metal compound also forms a single-phase structure and easy-to-process alloy phase with the design alloy of the invention;
zr element is easy to oxidize, is difficult to realize uniform distribution in a matrix, has low solid solubility in copper, forms a copper-zirconium phase with copper, and is not beneficial to processing deformation;
The solid solubility of Cr element in copper is small, and a second phase which is rich in iron and separated out is easy to form at room temperature, so that the corrosion performance of the alloy is reduced, and the service life of the alloy in seawater is prolonged;
The Co metal raw material has a higher melting point, and the brass alloy has an extremely low melting point, is not easy to add into the alloy and is uniformly dispersed.
The inventors have found through a great deal of experiments that, with respect to the alloy formulation provided by the present invention, when the above elements are introduced therein, there is no benefit to the final effect, even the various properties are degraded, and at the same time, the alloy components and the subsequent preparation process are complicated, adding additional cost. The alloy formula provided by the invention has the advantages that higher plasticity and excellent repeated bending performance are realized by simpler alloy components, and the problems that the existing copper alloy wire is more in element types, difficult to process and the like are effectively solved.
Based on the foregoing, the inventors have further preferred several more preferred embodiments, namely, the copper alloy wire comprises the following components in weight percent: 68 to 75 weight percent of Cu, 0.5 to 1.2 weight percent of Sn, 0.8 to 1.5 weight percent of Al, 0.1 to 0.3 weight percent of Ti, 0.2 to 0.8 weight percent of Si, and the balance of Zn and unavoidable impurity elements, wherein the components of the copper alloy wire do not comprise Ni, fe, mg, B, zr, cr and Co; in the copper alloy wire, 25< [ Zn ] eq. <36.
To further optimize the alloy formulation, in a typical embodiment, the composition of the copper alloy wire is such that the weight ratio of Al to Ti is (3-10): 1. the inventor obtains the weight relation through a large number of experiments, analyzes that the Al and Ti elements can form AlxTiy compounds respectively, and needs excessive Al element to exert the effect of the Al element on improving the corrosion resistance, and optimizes the Al/Ti ratio to (3-10) to more effectively slow down the corrosion rate of the copper alloy wire and improve the corrosion resistance.
In a preferred embodiment, the grain size of the copper alloy wire is 30-80 μm, and by optimizing the grain size, the corrosion rate is effectively reduced, and the plasticity of the copper alloy wire is obviously improved.
In several exemplary embodiments, the copper alloy wire comprises the following components in weight percent: 70wt% of Cu, 1.2wt% of Sn, 0.8wt% of Al, 0.2wt% of Ti, 0.4wt% of Si, and the balance of Zn and unavoidable impurity elements, wherein [ Zn ] eq. =35.5 in the copper alloy wire; or, the copper alloy wire comprises the following components in percentage by weight: 75wt% of Cu, 1.0wt% of Sn, 1.0wt% of Al, 0.3wt% of Ti, 0.8wt% of Si, and the balance of Zn and unavoidable impurity elements, wherein [ Zn ] eq. =33.6 in the copper alloy wire. The inventor selects the above alloy formulas through a large number of experiments, when the element compositions of the copper alloy wire are the two alloy formulas and the virtual zinc equivalent is the two values, the corrosion resistance is further improved, the annual corrosion rate is not higher than 0.01mm/a, and the service life is longer.
The invention also provides a preparation method of the copper alloy wire, which comprises the following steps: step S1, melting and alloying: raw materials are put into a smelting device to be melted, and copper alloy melt is obtained; step S2, electromagnetic horizontal continuous casting: carrying out electromagnetic horizontal continuous casting on the copper alloy melt to obtain a copper alloy casting rod, wherein the temperature of electromagnetic horizontal continuous casting is 1100-1150 ℃; the electromagnetic horizontal continuous casting is carried out in a continuous casting crystallizer, the alternating electromagnetic field current of the continuous casting crystallizer is 20-100A, and the frequency is 20-50 Hz; step S3, deformation and heat treatment: and sequentially carrying out rolling treatment, first annealing treatment, first cold drawing treatment, surface peeling treatment, second annealing treatment and second cold drawing treatment on the copper alloy cast rod to obtain the copper alloy wire.
In the preparation method provided by the invention, raw materials are smelted according to an alloy formula, then are molded by electromagnetic horizontal continuous casting with strictly controlled temperature, and then pass through rolling treatment, first annealing treatment, first cold drawing treatment, surface peeling treatment, second annealing treatment and second cold drawing treatment in sequence to obtain the finished copper alloy wire. The invention strictly controls the continuous casting temperature to 1100-1150 ℃, can effectively reduce burning loss of the copper alloy melt due to the temperature range, improves the yield, has better fluidity and is convenient for continuous casting. The copper alloy cast rod after initial molding is subjected to multiple cold deformation and annealing treatments, so that the grain size of the alloy is better controlled, the corrosion resistance is optimized, meanwhile, the surface smoothness and quality are controlled by carrying out surface peeling treatment after the second cold drawing treatment and before the second annealing treatment, and the plasticity and the machinability of the copper alloy cast rod are improved, so that the copper alloy wire capable of combining the corrosion resistance and the mechanical plasticity is obtained.
And aiming at the copper alloy formula provided by the invention, the special Si element can improve the alloy strength, and the Ti element is beneficial to refining the as-cast crystal grains, so that the alloy has higher strength and processability under the condition of keeping a single-phase structure to the maximum extent, and the application in the marine environment is satisfied. Accordingly, in the process of preparing and forming, the mode of rolling and forming is used for the initial cast rod in advance, compared with the cold-drawing deformation processing mode, the method has higher processing efficiency, is more beneficial to the uniformity of wire interface deformation, and has better comprehensive performance while reducing the cost.
In the preparation process, aiming at the alloy formula provided by the invention, the inventor selects an electromagnetic horizontal continuous casting mode through a large number of experiments and comparison, and the casting mode can be better matched with the alloy formula provided by the invention, so that a casting rod with finer crystal grains and better performance is obtained, and the subsequent processes such as forming and the like are facilitated to be smoothly carried out; the alternating magnetic field current adopted by the electromagnetic horizontal continuous casting process is 20-100A, and the frequency is 20-50 Hz. In principle, each parameter in the electromagnetic horizontal continuous casting process can be adjusted conventionally, but the inventor aims at the alloy components provided by the invention through a large amount of experiments, and simultaneously, the parameter setting is preferably selected by matching with each subsequent process condition so as to further improve each performance of the obtained homoalloy wire.
In a preferred embodiment, the copper alloy cast rod in step S2 has a diameter of 15 to 20mm and a grain size of 200 to 500. Mu.m. As described above, the invention strictly controls the casting temperature in the electromagnetic horizontal continuous casting process, and further optimizes the diameter and grain size of the obtained copper alloy casting rod to be in the above range on the basis of the casting temperature, thereby improving the corrosion resistance and plasticity of the copper alloy wire more effectively. In a more preferred embodiment, the copper alloy casting bar has a diameter of 15-18 mm and a grain size of 250-450 μm, and based on the above, the inventors further conducted a number of experiments to optimize the grain size of the casting bar, and found that, with respect to the copper alloy wire provided by the present invention, a wire having finer grains and superior final corrosion performance can be obtained by electromagnetic continuous casting, while when the grain size of the initial casting bar is within this range, the subsequent process can be better matched and the corrosion resistance of the finally obtained wire can be more effectively improved.
Further, in order to make the deformation processing of each stage more compatible, the inventors have made a large number of experiments, and it is preferable that the deformation amount of the rolling processing in step S3 is 75 to 95%; the deformation of the first cold drawing treatment is 50-70%; the deformation of the second cold drawing treatment is 25-40%; and the fact that when the three deformation treatments are combined according to the deformation amounts is found, the processability of the obtained copper alloy intermediate casting rod can be better exerted, so that grains can be more effectively refined, performance degradation caused by unreasonable parameters or improper combination in the processing process is reduced, and various performances of the obtained copper alloy wire are improved.
In several more preferred embodiments, in step S3, the temperature of the first annealing treatment is 550 to 650 ℃ and the holding time is 2 to 6 hours, to obtain a first annealed wire; the grain size of the first annealed wire is 100-120 mu m; the temperature of the second annealing treatment is 500-650 ℃, and the heat preservation time is 2-6 hours, so as to obtain a second annealing wire; the grain size of the second annealed wire is 30-80 μm. Through a large number of experiments, the inventor further optimizes various process conditions of the twice annealing treatment, and matches the related condition parameters in the mode, thereby realizing further optimization of alloy metallographic structure, further refining grains, and improving the plasticity and corrosion resistance of the copper alloy wire.
In order to more significantly optimize the metallographic structure, causing it to behave as a single alpha phase, in a typical embodiment, the step of melting and alloying in step S1 further comprises: s1-1, loading copper into a smelting device for first melting to obtain a first melt; s1-2, adding silicon into the first melt, and performing second melting to obtain a second melt; s1-3, cooling the second melt to 1100-1150 ℃, sequentially adding tin, aluminum, zinc and copper-titanium intermediate alloy into the second melt, and performing third melting to obtain a copper alloy melt; the raw materials are subjected to alloy preparation according to the feeding sequence and the process conditions, so that the generation of a single alpha-phase solid solution can be more effectively realized, and a copper alloy melt with purer phase structure is obtained, thereby being beneficial to the subsequent improvement of comprehensive mechanical properties and corrosion resistance. More preferably, the first and second melts are each independently at a temperature of 1200 to 1240 ℃ and the third melt is at a temperature of 1100 to 1150 ℃. The temperature of the three smelting processes are matched with each other, so that each metal simple substance and intermediate alloy can be melted into the copper alloy melt at a proper speed, burning loss is effectively reduced, yield is improved, and uniformity of components and tissues is improved. In particular, the second melt is cooled to 1100-1150 ℃ before adding tin, aluminum, zinc and copper-titanium master alloys and performing a third melting, in order to facilitate the addition of low melting point metals and reduce the oxidation burn-out of the metals, so that these elements are reduced below this temperature before addition.
In a further aspect, the invention provides the application of the copper alloy wire in the field of marine culture, wherein the copper alloy wire is used as a corrosion-resistant marine culture net cage material, a net connecting and binding wire belt material.
The copper alloy provided by the invention has the advantages of high coordination of each alloy element, single metallographic structure and small grain size; the corrosion-resistant silk ribbon material has low annual corrosion rate of 0.009-0.03 mm/a (millimeter/year), good plasticity and repeated bending times of more than or equal to 5 times, and can be used as a corrosion-resistant silk ribbon material for net cage materials, net connection and bundling of marine culture.
The application is described in further detail below in connection with specific examples which are not to be construed as limiting the scope of the application as claimed.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Example 1
A preparation method of a copper alloy wire comprises the following steps:
(1) Melting and alloying: putting raw material Cu into a smelting device for first melting, adding pure silicon for second melting, standing until the raw material Cu is completely melted, cooling to 1100 ℃, sequentially adding pure tin, pure aluminum, pure zinc and Cu-10wt.% Ti intermediate alloy, and performing third melting to obtain a copper alloy melt;
(2) Electromagnetic horizontal continuous casting: adding an electromagnetic field at the front end of the crystallizer, and carrying out electromagnetic horizontal continuous casting on the copper alloy melt to obtain a copper alloy casting rod;
(3) And (3) carrying out deformation and heat treatment, namely sequentially carrying out rolling, first recrystallization annealing, first cold drawing, surface peeling, second recrystallization annealing and second cold drawing on the copper alloy cast rod to obtain the copper alloy wire.
The alloy components and [ Zn ] eq. of the copper alloy wire are shown in Table 1, the technological parameters involved in the preparation process are shown in tables 2-1 and 2-2, and the dimensional change conditions (including macroscopic size and microscopic crystal grain) in the preparation process are shown in Table 3.
Examples 2 to 20
Examples 2 to 20 differ from example 1 in the alloy composition and process parameters, the composition and [ Zn ] eq. are shown in Table 1, and the process condition-related parameters are shown in tables 2-1, 2-2 and 3.
Comparative examples 1 to 9
Comparative examples 2 to 9 differ from comparative example 1 in the alloy composition and the process parameters, the composition and [ Zn ] eq. are shown in Table 1, and the process condition-related parameters are shown in tables 2-1, 2-2 and 3.
TABLE 1
In table 1, comparative example 3, based on the data in the table, was added with 0.5wt.% Ni; comparative example 4 0.2wt.% Mg was added based on the data in the table; comparative example 5 added 0.05wt.% B based on the data in the table; comparative example 6 was added with 0.05wt.% Zr based on the data in the table; comparative example 7, based on the data in the table, added 0.5wt.% Cr; comparative example 8 0.5wt.% Co was added based on the data in the table.
TABLE 2-1
Wherein, in the casting process, the comparative example 1 and the comparative example 2 are stirred without adding electromagnetic field to refine the as-cast crystal grains.
TABLE 2-2
Performance test:
Grain size: and (3) selecting an as-cast cross section and a solid solution sample according to test requirements, longitudinally preparing the sample, measuring by using an EBSD (electron back scattering diffraction method), selecting proper test areas and proper step sizes in each state, and taking boundaries with orientation differences of more than 15 degrees as grain boundary statistical average grain sizes.
Rate of annual corrosion: immersing the sample in sea water of the sea area of the east or south sea for 3 months, 6 months, 9 months and 12 months, taking back the sample, cleaning and drying, measuring the weight difference, and calculating the annual corrosion rate through the mass difference and the surface area.
The dezincification corrosion depth test method comprises the following steps: each sample was immersed in an aqueous solution of CuCl 2 (10 g/L) at 75℃for 24 hours, and then taken out for measurement.
Number of repeated bending: and (3) fixing one end of the sample, bending the sample by 90 degrees around a cylindrical roller with a specified radius, and then performing repeated bending test of bending in the opposite direction to calculate the bending times when cracks appear.
The copper alloy wires obtained in each of the above examples and comparative examples were subjected to the above performance tests, and the results of each test are shown in tables 3 and 4, respectively.
TABLE 3 Table 3
TABLE 4 Table 4
From the above description, it can be seen that the Sn, al, si, ti element is added to the single-phase brass alloy, not only the strength and corrosion resistance of the alloy are improved, but also the added Si element is effective to improve the strength of the alloy to improve the seawater scouring resistance. The alloy element is added to obtain a single-phase structure in the matrix, so that the single-phase structure has higher plasticity, the repeated bending performance of the alloy is improved, and the problems of more element types, difficult processing and the like are effectively solved. Meanwhile, the copper alloy wire provided by the invention does not comprise Ni, fe, mg, B, zr, cr and Co, so that a compound formed by the copper alloy wire and alloy elements is avoided, a single-phase structure is formed by the copper alloy wire and the alloy designed by the invention, the alloy is easy to process, and the formed second phase reduces corrosion resistance.
According to the embodiment of the invention, the Ti element and the electromagnetic horizontal continuous casting refined cast crystal grain are added, the average size of alloy alpha-phase crystal grains is effectively regulated and controlled by combining deformation and recrystallization annealing, the average crystal grain size of a finished product is controlled to be 30-80 mu m, the corrosion rate can be controlled by controlling the crystal grain size, the regulation and control of the annual corrosion rate to be 0.009-0.03 mm/a (millimeter/year) is realized, the repeated bending times of the wire are more than or equal to 5 times, and the method is suitable for connecting and binding wires of net boxes and net jackets of different sea areas.
It should be noted that the terms "first," "second," and the like in the description and in the claims are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the application described herein are, for example, capable of operation in sequences other than those described herein.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The copper alloy wire is characterized by comprising the following components in percentage by weight: 65-85 wt% of Cu, 0.5-2 wt% of Sn, 0.2-2.0 wt% of Al, 0.05-0.5 wt% of Ti, 0.05-1.5 wt% of Si, and the balance of Zn and unavoidable impurity elements;
In the copper alloy wire, 20< [ Zn ] eq. <38;
[ Zn ] eq. =100 ([ Zn ] + [ M ])/([ Zn ] + [ M ] + [ Cu ]), [ M ] =2 ] [ Sn ] +6 [ Al ] -10 [ Si ]; [ Zn ] is the actual content of the Zn element, [ Cu ] is the actual content of the Cu element, [ Sn ] is the actual content of the Sn element, [ Al ] is the actual content of the Al element, [ Si ] is the actual content of the Si element;
the metallographic structure of the copper alloy wire is a single alpha phase;
The preparation method of the copper alloy wire comprises the following steps:
step S1, melting and alloying: raw materials are put into a smelting device to be melted, and copper alloy melt is obtained;
Step S2, electromagnetic horizontal continuous casting: carrying out electromagnetic horizontal continuous casting on the copper alloy melt to obtain a copper alloy casting rod, wherein the temperature of the electromagnetic horizontal continuous casting is 1100-1150 ℃; the electromagnetic horizontal continuous casting is carried out in a continuous casting crystallizer, the alternating electromagnetic field current of the continuous casting crystallizer is 20-100A, and the frequency is 20-50 Hz;
step S3, deformation and heat treatment: sequentially carrying out rolling treatment, first annealing treatment, first cold drawing treatment, surface peeling treatment, second annealing treatment and second cold drawing treatment on the copper alloy cast rod to obtain the copper alloy wire;
The deformation of the rolling treatment is 75-95%;
the temperature of the first annealing treatment is 550-650 ℃, and the heat preservation time is 2-6 hours.
2. The copper alloy wire according to claim 1, wherein the copper alloy wire comprises the following components in percentage by weight: 68-75 wt% of Cu, 0.5-1.2 wt% of Sn, 0.8-1.5 wt% of Al, 0.1-0.3 wt% of Ti, 0.2-0.8 wt% of Si, and the balance of Zn and unavoidable impurity elements;
In the copper alloy wire, 25< [ Zn ] eq. <36.
3. The copper alloy wire according to claim 2, wherein the weight ratio of Al to Ti in the composition of the copper alloy wire is (3 to 10): 1.
4. The copper alloy wire according to claim 3, wherein the grain size of the copper alloy wire is 30 to 80 μm.
5. The copper alloy wire according to claim 1, wherein the copper alloy cast rod in the step S2 has a diameter of 15 to 20mm and a grain size of 200 to 500 μm.
6. The copper alloy wire according to claim 5, wherein in the step S3,
The deformation of the first cold drawing treatment is 50-70%;
the deformation of the second cold drawing treatment is 25-40%.
7. The copper alloy wire according to claim 6, wherein in the step S3,
The grain size of the first annealed wire is 100-120 mu m; the temperature of the second annealing treatment is 500-650 ℃, and the heat preservation time is 2-6 hours, so that a second annealing wire material is obtained; the grain size of the second annealed wire is 30-80 mu m.
8. The copper alloy wire according to claim 7, wherein the step of melting and alloying in step S1 further comprises:
s1-1, loading copper into a smelting device for first melting to obtain a first melt;
S1-2, adding silicon into the first melt, and performing second melting to obtain a second melt;
S1-3, cooling the second melt to 1100-1150 ℃, sequentially adding tin, aluminum, zinc and copper-titanium intermediate alloy into the second melt, and performing third melting to obtain the copper alloy melt;
The temperature of the first melting and the second melting is 1200-1240 ℃ respectively and independently, and the temperature of the third melting is 1100-1150 ℃.
9. Use of a copper alloy wire according to any one of claims 1 to 4 as corrosion resistant marine aquaculture net cage material, net attachment and strapping tape in the field of marine aquaculture.
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| CN116140564A (en) * | 2022-09-09 | 2023-05-23 | 昆明冶金研究院有限公司北京分公司 | Electromagnetic horizontal continuous casting device and method for high-tin wide-width tin phosphor bronze alloy strip blank |
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