CN113373344A - High-performance zinc white copper and preparation method thereof - Google Patents

High-performance zinc white copper and preparation method thereof Download PDF

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Publication number
CN113373344A
CN113373344A CN202110636042.4A CN202110636042A CN113373344A CN 113373344 A CN113373344 A CN 113373344A CN 202110636042 A CN202110636042 A CN 202110636042A CN 113373344 A CN113373344 A CN 113373344A
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China
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washing
strip
plate strip
carrying
sulfuric acid
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王建立
曹袆程
李钊
楼祺君
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Zhejiang Weijing New Material Co ltd
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Zhejiang Weijing New Material Co ltd
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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
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B37/00—Control devices or methods specially adapted for metal-rolling mills or the work produced thereby
    • B21B37/74—Temperature control, e.g. by cooling or heating the rolls or the product
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • 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
    • C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • 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
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals
    • C23G1/103—Other heavy metals copper or alloys of copper
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G3/00—Apparatus for cleaning or pickling metallic material
    • C23G3/02—Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously

Abstract

The invention provides high-performance zinc white copper and a preparation method thereof, and relates to the technical field of alloy materials. The high-performance zinc white copper provided by the invention comprises the following chemical components in percentage by mass: 16.5-19.5% of nickel, 12-20% of zinc, 0.1-0.25% of iron, 0.2-0.5% of manganese, 0-0.05% of lead and the balance of copper. The high-performance zinc white copper provided by the invention has the advantages of higher strength, hardness, glossiness and brazing performance, and low grain size and roughness.

Description

High-performance zinc white copper and preparation method thereof
Technical Field
The invention relates to the technical field of alloy materials, in particular to high-performance zinc white copper and a preparation method thereof.
Background
The zinc white copper is commonly used as various parts in precision instruments, medical instruments and communication engineering due to good corrosion resistance, excellent pressure processing performance and welding performance and silvery white bright appearance, and the zinc white copper is also used for replacing the traditional brass material in the spectacle manufacturing industry to manufacture middle and high-grade spectacle frames.
At present, the existing zinc-copper-nickel alloy in China still has some problems, such as low strength, low hardness, poor wear resistance, large friction coefficient, short service life, poor surface glossiness and the like, and can not meet the multi-angle and all-round requirements put forward by the market. With the rapid development of modern electronics and communication industries, the high shielding property of mobile communication and the high reliable sealing property of a small relay crystal resonator shell, strict performance and quality requirements are provided for the zinc-copper-nickel alloy material, so that the development of a new zinc-copper-nickel alloy material matched with different performance requirements is particularly necessary.
Disclosure of Invention
The invention aims to provide high-performance zinc white copper and a preparation method thereof, and the high-performance zinc white copper provided by the invention has the advantages of high strength, high hardness, high glossiness, low roughness and low grain size, and can meet the requirements of various industrial fields on zinc white copper alloy materials.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a high-performance zinc white copper which comprises the following chemical components in percentage by mass: 16.5-19.5% of nickel, 12-20% of zinc, 0.1-0.25% of iron, 0.2-0.5% of manganese, 0-0.05% of lead and the balance of copper.
Preferably, the chemical composition of the high-performance zinc white copper comprises the following components in percentage by mass: 17.25-18.75% of nickel, 14-18% of zinc, 0.137-0.213% of iron, 0.275-0.425% of manganese, 0.013-0.038% of lead and the balance of copper.
The invention provides a preparation method of high-performance zinc white copper in the technical scheme, which comprises the following steps:
smelting and casting a metal raw material to obtain a casting blank; the chemical components of the metal raw material are consistent with those of the high-performance zinc white copper in the technical scheme;
cogging and blooming the casting blank to obtain a plate and strip;
carrying out first annealing on the plate strip to obtain a first annealed plate strip;
carrying out first cold rolling on the first annealing plate strip to obtain a first cold-rolled plate strip;
carrying out second annealing on the first cold-rolled plate strip to obtain a second annealed plate strip;
carrying out second cold rolling on the second annealing plate strip to obtain a second cold-rolled plate strip;
and carrying out third annealing on the second cold-rolled plate strip to obtain the high-performance zinc white copper.
Preferably, the smelting temperature is 1250-1300 ℃; the casting temperature is 1150-1200 ℃.
Preferably, the total deformation of the cogging blooming is 75-80%.
Preferably, the temperature of the first annealing is 600-700 ℃, and the heat preservation time is 5-7 h.
Preferably, the total deformation amount of the first cold rolling is 70-80%.
Preferably, the temperature of the second annealing is 550-600 ℃, and the heat preservation time is 6-8 h.
Preferably, the total deformation amount of the second cold rolling is 60-90%.
Preferably, the temperature of the third annealing is 540-580 ℃, and the heat preservation time is 6-8 h.
The invention provides a high-performance zinc white copper which comprises the following chemical components in percentage by mass: 16.5-19.5% of nickel, 12-20% of zinc, 0.1-0.25% of iron, 0.2-0.5% of manganese, 0-0.05% of lead and the balance of copper. In the invention, nickel and copper can form an infinite solid solution, the strength and the corrosion resistance of the alloy can be improved by adding nickel element, and the color of the alloy can be adjusted; the zinc element has higher solubility in the copper-nickel solid solution and stronger solid solution strengthening effect, and the zinc element is added to improve the strength, hardness and corrosion resistance of the copper-nickel alloy; the addition of iron element can improve the strength and hardness of the alloy by refining grains and delaying the recrystallization process; the manganese element and the nickel element can form a nickel-manganese compound, so that the nickel-manganese compound has a precipitation strengthening effect, the strength, corrosion resistance and elasticity of the alloy can be improved by adding the manganese element, the dezincification of the zinc-copper alloy can be prevented, and the stability of a high-temperature structure can be improved; the addition of lead element can improve the cutting performance of the zinc-copper-nickel alloy.
Compared with other zinc white copper alloys, the high-performance zinc white copper provided by the invention has the advantages of higher strength, hardness, glossiness and brazing performance, and low grain size and roughness. The embodiment result shows that the high-performance zinc white copper provided by the invention has the tensile strength of 350-750 MPa, the hardness of 85-220 HV, the glossiness range of 200-500 GU, the tin coating rate of more than 95%, the grain size of 0.008-0.035 mm and the roughness of less than 0.15 mu m; meanwhile, the heat preservation time of 270 ℃ for 4min can reach at least two times of non-oxidation yellowing, and the method can be widely applied to resonator shells, mobile phone shielding cases, musical instrument metal components, crystal oscillator tubes, clocks and other precision parts and medical instrument parts.
Detailed Description
The invention provides a high-performance zinc white copper which comprises the following chemical components in percentage by mass: 16.5-19.5% of nickel, 12-20% of zinc, 0.1-0.25% of iron, 0.2-0.5% of manganese, 0-0.05% of lead and the balance of copper.
The high-performance zinc white copper provided by the invention comprises 16.5-19.5% of nickel, preferably 17.25-18.75%, and further preferably 18% by mass.
The high-performance zinc white copper provided by the invention comprises 12-20% of zinc, preferably 14-18% of zinc, and further preferably 16% of zinc by mass.
The high-performance zinc white copper provided by the invention comprises 0.1-0.25% of iron, preferably 0.137-0.213%, and more preferably 0.175-0.200% by mass.
The high-performance zinc white copper provided by the invention comprises 0.2-0.5% of manganese, preferably 0.275-0.425%, and further preferably 0.35-0.40% by mass.
The high-performance zinc white copper provided by the invention comprises 0-0.05% of lead, preferably 0.013-0.038%, and further preferably 0.025% by mass.
The high-performance zinc white copper provided by the invention preferably further comprises inevitable impurities. The total mass content of the unavoidable impurities is preferably < 0.01% by mass.
The high-performance zinc white copper provided by the invention comprises the balance of copper.
The invention also provides a preparation method of the high-performance zinc white copper in the technical scheme, which comprises the following steps:
smelting and casting a metal raw material to obtain a casting blank; the chemical components of the metal raw material are consistent with those of the high-performance zinc white copper in the technical scheme;
cogging and blooming the casting blank to obtain a plate and strip;
carrying out first annealing on the plate strip to obtain a first annealed plate strip;
carrying out first cold rolling on the first annealing plate strip to obtain a first cold-rolled plate strip;
carrying out second annealing on the first cold-rolled plate strip to obtain a second annealed plate strip;
carrying out second cold rolling on the second annealing plate strip to obtain a second cold-rolled plate strip;
and carrying out third annealing on the second cold-rolled plate strip to obtain the high-performance zinc white copper.
The invention carries out smelting and casting on metal raw materials to obtain a casting blank. In the present invention, the metal raw material preferably includes pure nickel, electrolytic copper, copper-manganese alloy, and pure zinc. The invention has no special requirement on the specific proportion of the metal raw materials, and the chemical components of the metal raw materials are consistent with those of the high-performance zinc cupronickel in the technical scheme.
The smelting and casting are preferably carried out in a horizontal continuous casting mode. In the invention, the smelting equipment is preferably a power frequency induction furnace. When the smelting is carried out, the adding sequence of the metal raw materials preferably comprises pure nickel, electrolytic copper, copper-manganese alloy and pure zinc in sequence. The invention can reduce the material loss and improve the component uniformity of the melt by adopting the feeding sequence.
In the invention, the smelting temperature is preferably 1250-1300 ℃, more preferably 1260-1280 ℃, and further preferably 1275 ℃; the heat preservation time at the smelting temperature is preferably 5-30 min, and more preferably 15-20 min. In the invention, the casting temperature is preferably 1150-1200 ℃, and more preferably 1175-1180 ℃.
After a casting blank is obtained, the casting blank is cogging and blooming to obtain a plate and strip. In the invention, the total deformation of the cogging blooming is preferably 75-80%, and more preferably 80%. In the present invention, the transformation of the as-cast structure of the material into the processed structure is facilitated by the cogging.
According to the invention, the casting blank is preferably subjected to surface milling treatment before cogging and blooming. The surface defects of the casting blank are removed through surface milling treatment. In the invention, the upper and lower milling surface amount of the milling surface treatment is preferably 1 mm.
In a specific embodiment of the invention, the strip of sheet metal after the cogging is preferably trimmed and then subjected to a first annealing. In the present invention, the amount of the cut edge is preferably 5mm, and the deformed uneven portion in rolling is removed.
After the plate strip is obtained, the plate strip is subjected to first annealing to obtain a first annealed plate strip. In the invention, the temperature of the first annealing is preferably 600-700 ℃, and more preferably 625-650 ℃; the heat preservation time is preferably 5-7 h, and more preferably 6 h. In the present invention, the atmosphere of the first annealing is preferably 25 to 75% by volume of hydrogen and the balance of nitrogen. In the present invention, the first annealing is preferably a bell-type annealing. In the invention, the first annealing can transform the material from the processing structure to the recrystallization structure and recover the plasticity of the material so as to facilitate the subsequent processing of the material.
After the first annealing plate strip is obtained, the first annealing plate strip is subjected to first cold rolling to obtain a first cold-rolled plate strip.
In the present invention, the total deformation amount of the first cold rolling is preferably 70 to 80%, and more preferably 75%. In the present invention, the temperature of the first cold rolling is preferably 35 to 40 ℃, and more preferably 38 ℃.
According to the invention, the first annealed sheet strip is preferably subjected to a first pickling before the first cold rolling. In the present invention, the first acid washing preferably includes sulfuric acid washing, water washing, and passivating agent washing in this order. In the invention, the mass concentration of the sulfuric acid solution for sulfuric acid washing is preferably 10-25%, and more preferably 15-20%; the passivating agent for washing is preferably benzotriazole water solution; the mass concentration of the passivating agent is preferably 0.03-0.30%, and more preferably 0.10-0.20%. The oxide layer on the surface of the first annealing plate strip is removed by using first acid cleaning.
After the first cold-rolled plate strip is obtained, the first cold-rolled plate strip is subjected to second annealing to obtain a second annealed plate strip. In the invention, the temperature of the second annealing is preferably 550-600 ℃, and more preferably 575 ℃; the heat preservation time is preferably 6-8 h, and more preferably 7 h. In the present invention, the atmosphere of the second annealing is preferably 25 to 75% by volume of hydrogen and the balance of nitrogen. In the present invention, the second annealing is preferably a bell-type annealing.
After the second annealing plate strip is obtained, the second annealing plate strip is subjected to second cold rolling to obtain a second cold-rolled plate strip. In the present invention, the total deformation amount of the second cold rolling is preferably 60 to 90%, more preferably 65 to 80%, and further preferably 70 to 75%. In the invention, the temperature of the second cold rolling is preferably 35-40 ℃, and more preferably 37-38 ℃.
The invention preferably subjects the second annealed sheet strip to a second pickling before the second cold rolling. In the present invention, the second acid washing preferably includes sulfuric acid washing, water washing, and passivating agent washing in this order. In the invention, the mass concentration of the sulfuric acid solution for sulfuric acid washing is preferably 10-25%, and more preferably 15-20%; the passivating agent for washing is preferably benzotriazole water solution; the mass concentration of the passivating agent is preferably 0.03-0.30%, and more preferably 0.10-0.20%. The oxide layer on the surface of the first annealing plate strip is removed by using first acid cleaning.
After the second cold-rolled plate strip is obtained, the third annealing is carried out on the second cold-rolled plate strip to obtain the high-performance zinc white copper. In the invention, the temperature of the third annealing is preferably 540-580 ℃, and more preferably 560 ℃; the heat preservation time is preferably 6-8 h, and more preferably 7 h. In the present invention, the atmosphere of the third annealing is preferably 75% by volume of hydrogen and 25% by volume of nitrogen. In the present invention, the third annealing is preferably a bell-type annealing.
According to the invention, after the third annealing is carried out, the third annealed sheet strip is preferably subjected to third acid cleaning to obtain the high-performance zinc white copper. In the present invention, the third acid washing preferably includes sulfuric acid washing, water washing, and passivating agent washing in this order. In the invention, the mass concentration of the sulfuric acid solution for sulfuric acid washing is preferably 5-20%, and more preferably 8-15%; the passivating agent for washing is preferably benzotriazole water solution; the mass concentration of the passivating agent is preferably 0.03-0.30%, and more preferably 0.10-0.20%. The oxide layer on the surface of the third annealing plate strip is removed by using a third acid washing.
According to the invention, the plate and strip obtained by the third pickling is preferably subjected to stretch bending straightening to obtain the high-performance zinc white copper. The high-performance zinc white copper prepared by the method is preferably a high-performance zinc white copper plate strip. In the present invention, the elongation of the stretch bending straightening is preferably 0.1 to 0.25%, and more preferably 0.18 to 0.20%. In the present invention, stretch bending straightening is used to equalize the internal stress of the material and to level the flatness of the strip.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The high-performance zinc white copper of the embodiment is prepared by adopting the following metal raw materials: pure nickel, electrolytic copper, copper-manganese alloy and pure zinc; the chemical composition of the high-performance zinc white copper is shown in table 1.
Smelting by adopting a power frequency induction furnace, wherein the adding sequence of the metal raw materials is as follows: heating pure nickel, electrolytic copper, copper-manganese alloy and pure zinc to 1250 ℃, preserving heat for 15min after the metal raw materials are completely melted, pouring the metal raw materials into a heat preservation furnace, and carrying out horizontal continuous casting to obtain a casting blank; the casting temperature during the horizontal continuous casting is 1175 ℃;
carrying out surface milling treatment on the casting blank, wherein the upper surface milling amount and the lower surface milling amount are 1 mm;
cogging and blooming the casting blank subjected to surface milling treatment, wherein the total deformation is 80%, and trimming the slab and strip subjected to cogging, wherein the trimming amount is 5mm to obtain the slab and strip;
carrying out bell-type annealing on the plate strip, wherein the annealing temperature is 600 ℃, the heat preservation time is 7h, and the annealing atmosphere is 25% by volume of hydrogen and 75% by volume of nitrogen to obtain a first annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the first annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 20%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so as to obtain a pickled sheet strip;
carrying out first cold rolling on the pickled plate strip, wherein the temperature of the first cold rolling is 35 ℃, and the total deformation is 80% to obtain a first cold-rolled plate strip;
carrying out bell-type annealing on the first cold-rolled plate strip, wherein the annealing temperature is 550 ℃, the heat preservation time is 8 hours, and the annealing atmosphere comprises 50% by volume of hydrogen and 50% by volume of nitrogen to obtain a second annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the second annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 20%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so that a second acid-washed sheet strip is obtained;
carrying out second cold rolling on the second acid washing plate strip, wherein the temperature of the second cold rolling is 37 ℃, and the total deformation is 80% to obtain a second cold rolling plate strip;
carrying out bell-type annealing on the second cold-rolled plate strip, wherein the annealing temperature is 540 ℃, the heat preservation time is 8 hours, and the protective gas is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a third annealed plate strip;
and sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the third annealed sheet and strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 10%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.15% of benzotriazole water solution, so that the high-performance zinc white copper is obtained.
The properties of the high performance zinc white copper prepared in this example are shown in table 2.
Example 2
The high-performance zinc white copper of the embodiment is prepared by adopting the following metal raw materials: pure nickel, electrolytic copper, copper-manganese alloy and pure zinc; the chemical composition of the high-performance zinc white copper is shown in table 1.
Smelting by adopting a power frequency induction furnace, wherein the adding sequence of the metal raw materials is as follows: heating pure nickel, electrolytic copper, copper-manganese alloy and pure zinc to 1300 ℃ until the metal raw materials are completely melted, preserving heat for 15min, pouring into a heat preserving furnace, and carrying out horizontal continuous casting to obtain a casting blank; the casting temperature during the horizontal continuous casting is 1200 ℃;
carrying out surface milling treatment on the casting blank, wherein the upper surface milling amount and the lower surface milling amount are 1 mm;
cogging and blooming the casting blank subjected to surface milling treatment, wherein the total deformation is 75%, and trimming the slab and strip subjected to cogging, wherein the trimming amount is 5mm to obtain the slab and strip;
carrying out bell-type annealing on the plate strip, wherein the annealing temperature is 700 ℃, the heat preservation time is 5h, and the annealing atmosphere comprises 50% by volume of hydrogen and 50% by volume of nitrogen to obtain a first annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the first annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 15%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so as to obtain a pickled sheet strip;
carrying out first cold rolling on the pickled plate strip, wherein the temperature of the first cold rolling is 40 ℃, and the total deformation is 70%, so as to obtain a first cold-rolled plate strip;
carrying out bell-type annealing on the first cold-rolled plate strip, wherein the annealing temperature is 600 ℃, the heat preservation time is 6 hours, and the annealing atmosphere is 25% by volume of hydrogen and 75% by volume of nitrogen to obtain a second annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the second annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 20%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so that a second acid-washed sheet strip is obtained;
carrying out second cold rolling on the second acid washing plate strip, wherein the temperature of the second cold rolling is 35 ℃, and the total deformation is 60% to obtain a second cold rolling plate strip;
carrying out bell-type annealing on the second cold-rolled plate strip, wherein the annealing temperature is 580 ℃, the heat preservation time is 6 hours, and the protective gas is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a third annealed plate strip;
and sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the third annealed sheet and strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 8%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.2% of benzotriazole water solution, so that the high-performance zinc white copper is obtained.
The properties of the high performance zinc white copper prepared in this example are shown in table 2.
Example 3
The high-performance zinc white copper of the embodiment is prepared by adopting the following metal raw materials: pure nickel, electrolytic copper, copper-manganese alloy and pure zinc; the chemical composition of the high-performance zinc white copper is shown in table 1.
Smelting by adopting a power frequency induction furnace, wherein the adding sequence of the metal raw materials is as follows: heating pure nickel, electrolytic copper, copper-manganese alloy and pure zinc to 1275 ℃ until the metal raw materials are completely melted, preserving heat for 15min, pouring into a heat preservation furnace, and carrying out horizontal continuous casting to obtain a casting blank; the casting temperature during the horizontal continuous casting is 1175 ℃;
carrying out surface milling treatment on the casting blank, wherein the upper surface milling amount and the lower surface milling amount are 1 mm;
cogging and blooming the casting blank subjected to surface milling treatment, wherein the total deformation is 80%, and trimming the slab and strip subjected to cogging, wherein the trimming amount is 5mm to obtain the slab and strip;
carrying out bell-type annealing on the plate strip, wherein the annealing temperature is 650 ℃, the heat preservation time is 6h, and the annealing atmosphere comprises 50% by volume of hydrogen and 50% by volume of nitrogen to obtain a first annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the first annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 15%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.15% of benzotriazole water solution, so as to obtain a pickled sheet strip;
carrying out first cold rolling on the pickled plate strip, wherein the temperature of the first cold rolling is 40 ℃, and the total deformation is 80% to obtain a first cold-rolled plate strip;
carrying out bell-type annealing on the first cold-rolled plate strip, wherein the annealing temperature is 575 ℃, the heat preservation time is 7h, and the annealing atmosphere is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a second annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the second annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 20%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so that a second acid-washed sheet strip is obtained;
carrying out second cold rolling on the second acid washing plate strip, wherein the temperature of the second cold rolling is 40 ℃, and the total deformation is 70%, so as to obtain a second cold rolling plate strip;
performing bell-type annealing on the second cold-rolled plate strip, wherein the annealing temperature is 560 ℃, the heat preservation time is 7 hours, and the protective gas is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a third annealed plate strip;
and sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the third annealed sheet and strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 15%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.15% of benzotriazole water solution, so that the high-performance zinc white copper is obtained.
The properties of the high performance zinc white copper prepared in this example are shown in table 2.
Example 4
The high-performance zinc white copper of the embodiment is prepared by adopting the following metal raw materials: pure nickel, electrolytic copper, copper-manganese alloy and pure zinc; the chemical composition of the high-performance zinc white copper is shown in table 1.
Smelting by adopting a power frequency induction furnace, wherein the adding sequence of the metal raw materials is as follows: heating pure nickel, electrolytic copper, copper-manganese alloy and pure zinc to 1260 ℃, keeping the temperature for 15min after the metal raw materials are completely melted, pouring the metal raw materials into a heat preservation furnace, and carrying out horizontal continuous casting to obtain a casting blank; the casting temperature during the horizontal continuous casting is 1175 ℃;
carrying out surface milling treatment on the casting blank, wherein the upper surface milling amount and the lower surface milling amount are 1 mm;
cogging and blooming the casting blank subjected to surface milling treatment, wherein the total deformation is 75%, and trimming the slab and strip subjected to cogging, wherein the trimming amount is 5mm to obtain the slab and strip;
carrying out bell-type annealing on the plate strip, wherein the annealing temperature is 625 ℃, the heat preservation time is 5 hours, and the annealing atmosphere is 50% by volume of hydrogen and 50% by volume of nitrogen to obtain a first annealing plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the first annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 15%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.15% of benzotriazole water solution, so as to obtain a pickled sheet strip;
carrying out first cold rolling on the pickled plate strip, wherein the temperature of the first cold rolling is 38 ℃, and the total deformation is 75% to obtain a first cold-rolled plate strip;
carrying out bell-type annealing on the first cold-rolled plate strip, wherein the annealing temperature is 550 ℃, the heat preservation time is 8 hours, and the annealing atmosphere is 25% by volume of hydrogen and 75% by volume of nitrogen to obtain a second annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the second annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 20%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so that a second acid-washed sheet strip is obtained;
carrying out second cold rolling on the second acid washing plate strip, wherein the temperature of the second cold rolling is 40 ℃, and the total deformation is 65%, so as to obtain a second cold rolling plate strip;
carrying out bell-type annealing on the second cold-rolled plate strip, wherein the annealing temperature is 540 ℃, the heat preservation time is 8 hours, and the protective gas is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a third annealed plate strip;
and sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the third annealed sheet and strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 12%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so that the high-performance zinc white copper is obtained.
The properties of the high performance zinc white copper prepared in this example are shown in table 2.
Example 5
The high-performance zinc white copper of the embodiment is prepared by adopting the following metal raw materials: pure nickel, electrolytic copper, copper-manganese alloy and pure zinc; the chemical composition of the high-performance zinc white copper is shown in table 1.
Smelting by adopting a power frequency induction furnace, wherein the adding sequence of the metal raw materials is as follows: heating pure nickel, electrolytic copper, copper-manganese alloy and pure zinc to 1280 ℃ until the metal raw materials are completely melted, preserving heat for 15min, pouring into a heat preserving furnace, and carrying out horizontal continuous casting to obtain a casting blank; the casting temperature during the horizontal continuous casting is 1200 ℃;
carrying out surface milling treatment on the casting blank, wherein the upper surface milling amount and the lower surface milling amount are 1 mm;
cogging and blooming the casting blank subjected to surface milling treatment, wherein the total deformation is 80%, and trimming the slab and strip subjected to cogging, wherein the trimming amount is 5mm to obtain the slab and strip;
carrying out bell-type annealing on the plate strip, wherein the annealing temperature is 700 ℃, the heat preservation time is 5h, and the annealing atmosphere is 25% by volume of hydrogen and 75% by volume of nitrogen to obtain a first annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the first annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 20%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.15% of benzotriazole water solution, so as to obtain a pickled sheet strip;
carrying out first cold rolling on the pickled plate strip, wherein the temperature of the first cold rolling is 40 ℃, and the total deformation is 75% to obtain a first cold-rolled plate strip;
carrying out bell-type annealing on the first cold-rolled plate strip, wherein the annealing temperature is 600 ℃, the heat preservation time is 7 hours, and the annealing atmosphere is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a second annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the second annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 20%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so that a second acid-washed sheet strip is obtained;
carrying out second cold rolling on the second acid washing plate strip, wherein the temperature of the second cold rolling is 40 ℃, and the total deformation is 60% to obtain a second cold rolling plate strip;
carrying out bell-type annealing on the second cold-rolled plate strip, wherein the annealing temperature is 580 ℃, the heat preservation time is 8 hours, and the protective gas is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a third annealed plate strip;
and sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the third annealed sheet and strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 10%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so that the high-performance zinc white copper is obtained.
The properties of the high performance zinc white copper prepared in this example are shown in table 2.
Example 6
The high-performance zinc white copper of the embodiment is prepared by adopting the following metal raw materials: pure nickel, electrolytic copper, copper-manganese alloy and pure zinc; the chemical composition of the high-performance zinc white copper is shown in table 1.
Smelting by adopting a power frequency induction furnace, wherein the adding sequence of the metal raw materials is as follows: heating pure nickel, electrolytic copper, copper-manganese alloy and pure zinc to 1250 ℃, preserving heat for 15min after the metal raw materials are completely melted, pouring the metal raw materials into a heat preservation furnace, and carrying out horizontal continuous casting to obtain a casting blank; the casting temperature during the horizontal continuous casting is 1175 ℃;
carrying out surface milling treatment on the casting blank, wherein the upper surface milling amount and the lower surface milling amount are 1 mm;
cogging and blooming the casting blank subjected to surface milling treatment, wherein the total deformation is 80%, and trimming the slab and strip subjected to cogging, wherein the trimming amount is 5mm to obtain the slab and strip;
carrying out bell-type annealing on the plate strip, wherein the annealing temperature is 700 ℃, the heat preservation time is 5h, and the annealing atmosphere comprises 50% by volume of hydrogen and 50% by volume of nitrogen to obtain a first annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the first annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 25%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.2% of benzotriazole water solution, so as to obtain a pickled sheet strip;
carrying out first cold rolling on the pickled plate strip, wherein the temperature of the first cold rolling is 35 ℃, and the total deformation is 80% to obtain a first cold-rolled plate strip;
carrying out bell-type annealing on the first cold-rolled plate strip, wherein the annealing temperature is 600 ℃, the heat preservation time is 6 hours, and the annealing atmosphere comprises 50% by volume of hydrogen and 50% by volume of nitrogen to obtain a second annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the second annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 20%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so that a second acid-washed sheet strip is obtained;
carrying out second cold rolling on the second acid washing plate strip, wherein the temperature of the second cold rolling is 35 ℃, and the total deformation is 80% to obtain a second cold rolling plate strip;
carrying out bell-type annealing on the second cold-rolled plate strip, wherein the annealing temperature is 580 ℃, the heat preservation time is 6 hours, and the protective gas is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a third annealed plate strip;
and sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the third annealed sheet and strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 8%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.15% of benzotriazole water solution, so that the high-performance zinc white copper is obtained.
The properties of the high performance zinc white copper prepared in this example are shown in table 2.
Example 7
The high-performance zinc white copper of the embodiment is prepared by adopting the following metal raw materials: pure nickel, electrolytic copper, copper-manganese alloy and pure zinc; the chemical composition of the high-performance zinc white copper is shown in table 1.
Smelting by adopting a power frequency induction furnace, wherein the adding sequence of the metal raw materials is as follows: heating pure nickel, electrolytic copper, copper-manganese alloy and pure zinc to 1250 ℃, preserving heat for 15min after the metal raw materials are completely melted, pouring the metal raw materials into a heat preservation furnace, and carrying out horizontal continuous casting to obtain a casting blank; the casting temperature during the horizontal continuous casting is 1175 ℃;
carrying out surface milling treatment on the casting blank, wherein the upper surface milling amount and the lower surface milling amount are 1 mm;
cogging and blooming the casting blank subjected to surface milling treatment, wherein the total deformation is 75%, and trimming the slab and strip subjected to cogging, wherein the trimming amount is 5mm to obtain the slab and strip;
carrying out bell-type annealing on the plate strip, wherein the annealing temperature is 600 ℃, the heat preservation time is 7h, and the annealing atmosphere comprises 50% by volume of hydrogen and 50% by volume of nitrogen to obtain a first annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the first annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 15%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.15% of benzotriazole water solution, so as to obtain a pickled sheet strip;
carrying out first cold rolling on the pickled plate strip, wherein the temperature of the first cold rolling is 40 ℃, and the total deformation is 80% to obtain a first cold-rolled plate strip;
carrying out bell-type annealing on the first cold-rolled plate strip, wherein the annealing temperature is 600 ℃, the heat preservation time is 8 hours, and the annealing atmosphere comprises 50% by volume of hydrogen and 50% by volume of nitrogen to obtain a second annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the second annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 20%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so that a second acid-washed sheet strip is obtained;
carrying out second cold rolling on the second acid washing plate strip, wherein the temperature of the second cold rolling is 38 ℃, and the total deformation is 90%, so as to obtain a second cold rolling plate strip;
carrying out bell-type annealing on the second cold-rolled plate strip, wherein the annealing temperature is 580 ℃, the heat preservation time is 8 hours, and the protective gas is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a third annealed plate strip;
and sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the third annealed sheet and strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 10%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.2% of benzotriazole water solution, so that the high-performance zinc white copper is obtained.
The properties of the high performance zinc white copper prepared in this example are shown in table 2.
Example 8
The high-performance zinc white copper of the embodiment is prepared by adopting the following metal raw materials: pure nickel, electrolytic copper, copper-manganese alloy and pure zinc; the chemical composition of the high-performance zinc white copper is shown in table 1.
Smelting by adopting a power frequency induction furnace, wherein the adding sequence of the metal raw materials is as follows: heating pure nickel, electrolytic copper, copper-manganese alloy and pure zinc to 1275 ℃ until the metal raw materials are completely melted, preserving heat for 15min, pouring into a heat preservation furnace, and carrying out horizontal continuous casting to obtain a casting blank; the casting temperature during the horizontal continuous casting is 1175 ℃;
carrying out surface milling treatment on the casting blank, wherein the upper surface milling amount and the lower surface milling amount are 1 mm;
cogging and blooming the casting blank subjected to surface milling treatment, wherein the total deformation is 80%, and trimming the slab and strip subjected to cogging, wherein the trimming amount is 5mm to obtain the slab and strip;
carrying out bell-type annealing on the plate strip, wherein the annealing temperature is 650 ℃, the heat preservation time is 5h, and the annealing atmosphere is 25% by volume of hydrogen and 75% by volume of nitrogen to obtain a first annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the first annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 20%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so as to obtain a pickled sheet strip;
carrying out first cold rolling on the pickled plate strip, wherein the temperature of the first cold rolling is 38 ℃, and the total deformation is 80% to obtain a first cold-rolled plate strip;
carrying out bell-type annealing on the first cold-rolled plate strip, wherein the annealing temperature is 550 ℃, the heat preservation time is 6 hours, and the annealing atmosphere comprises 50% by volume of hydrogen and 50% by volume of nitrogen to obtain a second annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the second annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 20%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so that a second acid-washed sheet strip is obtained;
carrying out second cold rolling on the second acid washing plate strip, wherein the temperature of the second cold rolling is 40 ℃, and the total deformation is 80% to obtain a second cold rolling plate strip;
carrying out bell-type annealing on the second cold-rolled plate strip, wherein the annealing temperature is 540 ℃, the heat preservation time is 6 hours, and the protective gas is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a third annealed plate strip;
and sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the third annealed sheet and strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 12%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.2% of benzotriazole water solution, so that the high-performance zinc white copper is obtained.
The properties of the high performance zinc white copper prepared in this example are shown in table 2.
Example 9
The high-performance zinc white copper of the embodiment is prepared by adopting the following metal raw materials: pure nickel, electrolytic copper, copper-manganese alloy and pure zinc; the chemical composition of the high-performance zinc white copper is shown in table 1.
Smelting by adopting a power frequency induction furnace, wherein the adding sequence of the metal raw materials is as follows: heating pure nickel, electrolytic copper, copper-manganese alloy and pure zinc to 1250 ℃, preserving heat for 15min after the metal raw materials are completely melted, pouring the metal raw materials into a heat preservation furnace, and carrying out horizontal continuous casting to obtain a casting blank; the casting temperature during the horizontal continuous casting is 1150 ℃;
carrying out surface milling treatment on the casting blank, wherein the upper surface milling amount and the lower surface milling amount are 1 mm;
cogging and blooming the casting blank subjected to surface milling treatment, wherein the total deformation is 75%, and trimming the slab and strip subjected to cogging, wherein the trimming amount is 5mm to obtain the slab and strip;
carrying out bell-type annealing on the plate strip, wherein the annealing temperature is 600 ℃, the heat preservation time is 7h, and the annealing atmosphere is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a first annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the first annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 10%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.15% of benzotriazole water solution, so as to obtain a pickled sheet strip;
carrying out first cold rolling on the pickled plate strip, wherein the temperature of the first cold rolling is 35 ℃, and the total deformation is 80% to obtain a first cold-rolled plate strip;
carrying out bell-type annealing on the first cold-rolled plate strip, wherein the annealing temperature is 600 ℃, the heat preservation time is 8 hours, and the annealing atmosphere is 25% by volume of hydrogen and 75% by volume of nitrogen to obtain a second annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the second annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 20%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so that a second acid-washed sheet strip is obtained;
carrying out second cold rolling on the second acid washing plate strip, wherein the temperature of the second cold rolling is 38 ℃, and the total deformation is 80% to obtain a second cold rolling plate strip;
carrying out bell-type annealing on the second cold-rolled plate strip, wherein the annealing temperature is 580 ℃, the heat preservation time is 8 hours, and the protective gas is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a third annealed plate strip;
and sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the third annealed sheet and strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 8%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.15% of benzotriazole water solution, so that the high-performance zinc white copper is obtained.
The properties of the high performance zinc white copper prepared in this example are shown in table 2.
Example 10
The high-performance zinc white copper of the embodiment is prepared by adopting the following metal raw materials: pure nickel, electrolytic copper, copper-manganese alloy and pure zinc; the chemical composition of the high-performance zinc white copper is shown in table 1.
Smelting by adopting a power frequency induction furnace, wherein the adding sequence of the metal raw materials is as follows: heating pure nickel, electrolytic copper, copper-manganese alloy and pure zinc to 1250 ℃, preserving heat for 15min after the metal raw materials are completely melted, pouring the metal raw materials into a heat preservation furnace, and carrying out horizontal continuous casting to obtain a casting blank; the casting temperature during the horizontal continuous casting is 1150 ℃;
carrying out surface milling treatment on the casting blank, wherein the upper surface milling amount and the lower surface milling amount are 1 mm;
cogging and blooming the casting blank subjected to surface milling treatment, wherein the total deformation is 80%, and trimming the slab and strip subjected to cogging, wherein the trimming amount is 5mm to obtain the slab and strip;
carrying out bell-type annealing on the plate strip, wherein the annealing temperature is 600 ℃, the heat preservation time is 5h, and the annealing atmosphere comprises 50% by volume of hydrogen and 50% by volume of nitrogen to obtain a first annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the first annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 10%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.2% of benzotriazole water solution, so as to obtain a pickled sheet strip;
carrying out first cold rolling on the pickled plate strip, wherein the temperature of the first cold rolling is 40 ℃, and the total deformation is 70%, so as to obtain a first cold-rolled plate strip;
carrying out bell-type annealing on the first cold-rolled plate strip, wherein the annealing temperature is 550 ℃, the heat preservation time is 6 hours, and the annealing atmosphere is 25% by volume of hydrogen and 75% by volume of nitrogen to obtain a second annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the second annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 20%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so that a second acid-washed sheet strip is obtained;
carrying out second cold rolling on the second acid washing plate strip, wherein the temperature of the second cold rolling is 40 ℃, and the total deformation is 60% to obtain a second cold rolling plate strip;
carrying out bell-type annealing on the second cold-rolled plate strip, wherein the annealing temperature is 540 ℃, the heat preservation time is 6 hours, and the protective gas is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a third annealed plate strip;
and sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the third annealed sheet and strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 12%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.15% of benzotriazole water solution, so that the high-performance zinc white copper is obtained.
The properties of the high performance zinc white copper prepared in this example are shown in table 2.
Example 11
The high-performance zinc white copper of the embodiment is prepared by adopting the following metal raw materials: pure nickel, electrolytic copper, copper-manganese alloy and pure zinc; the chemical composition of the high-performance zinc white copper is shown in table 1.
Smelting by adopting a power frequency induction furnace, wherein the adding sequence of the metal raw materials is as follows: heating pure nickel, electrolytic copper, copper-manganese alloy and pure zinc to 1300 ℃ until the metal raw materials are completely melted, preserving heat for 15min, pouring into a heat preserving furnace, and carrying out horizontal continuous casting to obtain a casting blank; the casting temperature during the horizontal continuous casting is 1175 ℃;
carrying out surface milling treatment on the casting blank, wherein the upper surface milling amount and the lower surface milling amount are 1 mm;
cogging and blooming the casting blank subjected to surface milling treatment, wherein the total deformation is 75%, and trimming the slab and strip subjected to cogging, wherein the trimming amount is 5mm to obtain the slab and strip;
carrying out bell-type annealing on the plate strip, wherein the annealing temperature is 700 ℃, the heat preservation time is 5h, and the annealing atmosphere comprises 50% by volume of hydrogen and 50% by volume of nitrogen to obtain a first annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the first annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 10%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.15% of benzotriazole water solution, so as to obtain a pickled sheet strip;
carrying out first cold rolling on the pickled plate strip, wherein the temperature of the first cold rolling is 35 ℃, and the total deformation is 80% to obtain a first cold-rolled plate strip;
carrying out bell-type annealing on the first cold-rolled plate strip, wherein the annealing temperature is 600 ℃, the heat preservation time is 6 hours, and the annealing atmosphere comprises 50% by volume of hydrogen and 50% by volume of nitrogen to obtain a second annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the second annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 20%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so that a second acid-washed sheet strip is obtained;
carrying out second cold rolling on the second acid washing plate strip, wherein the temperature of the second cold rolling is 40 ℃, and the total deformation is 80% to obtain a second cold rolling plate strip;
carrying out bell-type annealing on the second cold-rolled plate strip, wherein the annealing temperature is 580 ℃, the heat preservation time is 6 hours, and the protective gas is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a third annealed plate strip;
and sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the third annealed sheet and strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 15%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so that the high-performance zinc white copper is obtained.
The properties of the high performance zinc white copper prepared in this example are shown in table 2.
Example 12
The high-performance zinc white copper of the embodiment is prepared by adopting the following metal raw materials: pure nickel, electrolytic copper, copper-manganese alloy and pure zinc; the chemical composition of the high-performance zinc white copper is shown in table 1.
Smelting by adopting a power frequency induction furnace, wherein the adding sequence of the metal raw materials is as follows: heating pure nickel, electrolytic copper, copper-manganese alloy and pure zinc to 1300 ℃ until the metal raw materials are completely melted, preserving heat for 15min, pouring into a heat preserving furnace, and carrying out horizontal continuous casting to obtain a casting blank; the casting temperature during the horizontal continuous casting is 1200 ℃;
carrying out surface milling treatment on the casting blank, wherein the upper surface milling amount and the lower surface milling amount are 1 mm;
cogging and blooming the casting blank subjected to surface milling treatment, wherein the total deformation is 75%, and trimming the slab and strip subjected to cogging, wherein the trimming amount is 5mm to obtain the slab and strip;
carrying out bell-type annealing on the plate strip, wherein the annealing temperature is 700 ℃, the heat preservation time is 5h, and the annealing atmosphere is 25% by volume of hydrogen and 75% by volume of nitrogen to obtain a first annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the first annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 15%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so as to obtain a pickled sheet strip;
carrying out first cold rolling on the pickled plate strip, wherein the temperature of the first cold rolling is 35 ℃, and the total deformation is 70%, so as to obtain a first cold-rolled plate strip;
carrying out bell-type annealing on the first cold-rolled plate strip, wherein the annealing temperature is 550 ℃, the heat preservation time is 6 hours, and the annealing atmosphere is 25% by volume of hydrogen and 75% by volume of nitrogen to obtain a second annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the second annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 20%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so that a second acid-washed sheet strip is obtained;
carrying out second cold rolling on the second acid washing plate strip, wherein the temperature of the second cold rolling is 35 ℃, and the total deformation is 60% to obtain a second cold rolling plate strip;
carrying out bell-type annealing on the second cold-rolled plate strip, wherein the annealing temperature is 580 ℃, the heat preservation time is 6 hours, and the protective gas is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a third annealed plate strip;
and sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the third annealed sheet and strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 15%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.15% of benzotriazole water solution, so that the high-performance zinc white copper is obtained.
The properties of the high performance zinc white copper prepared in this example are shown in table 2.
Example 13
The high-performance zinc white copper of the embodiment is prepared by adopting the following metal raw materials: pure nickel, electrolytic copper, copper-manganese alloy and pure zinc; the chemical composition of the high-performance zinc white copper is shown in table 1.
Smelting by adopting a power frequency induction furnace, wherein the adding sequence of the metal raw materials is as follows: heating pure nickel, electrolytic copper, copper-manganese alloy and pure zinc to 1300 ℃ until the metal raw materials are completely melted, preserving heat for 15min, pouring into a heat preserving furnace, and carrying out horizontal continuous casting to obtain a casting blank; the casting temperature during the horizontal continuous casting is 1150 ℃;
carrying out surface milling treatment on the casting blank, wherein the upper surface milling amount and the lower surface milling amount are 1 mm;
cogging and blooming the casting blank subjected to surface milling treatment, wherein the total deformation is 80%, and trimming the slab and strip subjected to cogging, wherein the trimming amount is 5mm to obtain the slab and strip;
carrying out bell-type annealing on the plate strip, wherein the annealing temperature is 700 ℃, the heat preservation time is 7h, and the annealing atmosphere is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a first annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the first annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 15%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so as to obtain a pickled sheet strip;
carrying out first cold rolling on the pickled plate strip, wherein the temperature of the first cold rolling is 40 ℃, and the total deformation is 80% to obtain a first cold-rolled plate strip;
carrying out bell-type annealing on the first cold-rolled plate strip, wherein the annealing temperature is 600 ℃, the heat preservation time is 8 hours, and the annealing atmosphere is 25% by volume of hydrogen and 75% by volume of nitrogen to obtain a second annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the second annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 20%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so that a second acid-washed sheet strip is obtained;
carrying out second cold rolling on the second acid washing plate strip, wherein the temperature of the second cold rolling is 38 ℃, and the total deformation is 80% to obtain a second cold rolling plate strip;
carrying out bell-type annealing on the second cold-rolled plate strip, wherein the annealing temperature is 580 ℃, the heat preservation time is 8 hours, and the protective gas is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a third annealed plate strip;
and sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the third annealed sheet and strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 10%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so that the high-performance zinc white copper is obtained.
The properties of the high performance zinc white copper prepared in this example are shown in table 2.
Example 14
The high-performance zinc white copper of the embodiment is prepared by adopting the following metal raw materials: pure nickel, electrolytic copper, copper-manganese alloy and pure zinc; the chemical composition of the high-performance zinc white copper is shown in table 1.
Smelting by adopting a power frequency induction furnace, wherein the adding sequence of the metal raw materials is as follows: heating pure nickel, electrolytic copper, copper-manganese alloy and pure zinc to 1300 ℃ until the metal raw materials are completely melted, preserving heat for 15min, pouring into a heat preserving furnace, and carrying out horizontal continuous casting to obtain a casting blank; the casting temperature during the horizontal continuous casting is 1150 ℃;
carrying out surface milling treatment on the casting blank, wherein the upper surface milling amount and the lower surface milling amount are 1 mm;
cogging and blooming the casting blank subjected to surface milling treatment, wherein the total deformation is 75%, and trimming the slab and strip subjected to cogging, wherein the trimming amount is 5mm to obtain the slab and strip;
carrying out bell-type annealing on the plate strip, wherein the annealing temperature is 600 ℃, the heat preservation time is 5 hours, and the annealing atmosphere is 25% by volume of hydrogen and 75% by volume of nitrogen to obtain a first annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the first annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 15%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so as to obtain a pickled sheet strip;
carrying out first cold rolling on the pickled plate strip, wherein the temperature of the first cold rolling is 40 ℃, and the total deformation is 80% to obtain a first cold-rolled plate strip;
carrying out bell-type annealing on the first cold-rolled plate strip, wherein the annealing temperature is 550 ℃, the heat preservation time is 6 hours, and the annealing atmosphere comprises 50% by volume of hydrogen and 50% by volume of nitrogen to obtain a second annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the second annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 20%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so that a second acid-washed sheet strip is obtained;
carrying out second cold rolling on the second acid washing plate strip, wherein the temperature of the second cold rolling is 35 ℃, and the total deformation is 80% to obtain a second cold rolling plate strip;
carrying out bell-type annealing on the second cold-rolled plate strip, wherein the annealing temperature is 540 ℃, the heat preservation time is 6 hours, and the protective gas is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a third annealed plate strip;
and sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the third annealed sheet and strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 12%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.2% of benzotriazole water solution, so that the high-performance zinc white copper is obtained.
The properties of the high performance zinc white copper prepared in this example are shown in table 2.
Example 15
The high-performance zinc white copper of the embodiment is prepared by adopting the following metal raw materials: pure nickel, electrolytic copper, copper-manganese alloy and pure zinc; the chemical composition of the high-performance zinc white copper is shown in table 1.
Smelting by adopting a power frequency induction furnace, wherein the adding sequence of the metal raw materials is as follows: heating pure nickel, electrolytic copper, copper-manganese alloy and pure zinc to 1250 ℃, preserving heat for 15min after the metal raw materials are completely melted, pouring the metal raw materials into a heat preservation furnace, and carrying out horizontal continuous casting to obtain a casting blank; the casting temperature during the horizontal continuous casting is 1175 ℃;
carrying out surface milling treatment on the casting blank, wherein the upper surface milling amount and the lower surface milling amount are 1 mm;
cogging and blooming the casting blank subjected to surface milling treatment, wherein the total deformation is 80%, and trimming the slab and strip subjected to cogging, wherein the trimming amount is 5mm to obtain the slab and strip;
carrying out bell-type annealing on the plate strip, wherein the annealing temperature is 700 ℃, the heat preservation time is 5h, and the annealing atmosphere is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a first annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the first annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 20%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.15% of benzotriazole water solution, so as to obtain a pickled sheet strip;
carrying out first cold rolling on the pickled plate strip, wherein the temperature of the first cold rolling is 38 ℃, and the total deformation is 80% to obtain a first cold-rolled plate strip;
carrying out bell-type annealing on the first cold-rolled plate strip, wherein the annealing temperature is 550 ℃, the heat preservation time is 6 hours, and the annealing atmosphere is 25% by volume of hydrogen and 75% by volume of nitrogen to obtain a second annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the second annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 20%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so that a second acid-washed sheet strip is obtained;
carrying out second cold rolling on the second acid washing plate strip, wherein the temperature of the second cold rolling is 40 ℃, and the total deformation is 80% to obtain a second cold rolling plate strip;
carrying out bell-type annealing on the second cold-rolled plate strip, wherein the annealing temperature is 540 ℃, the heat preservation time is 6 hours, and the protective gas is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a third annealed plate strip;
and sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the third annealed sheet and strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 8%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.2% of benzotriazole water solution, so that the high-performance zinc white copper is obtained.
The properties of the high performance zinc white copper prepared in this example are shown in table 2.
Example 16
The high-performance zinc white copper of the embodiment is prepared by adopting the following metal raw materials: pure nickel, electrolytic copper, copper-manganese alloy and pure zinc; the chemical composition of the high-performance zinc white copper is shown in table 1.
Smelting by adopting a power frequency induction furnace, wherein the adding sequence of the metal raw materials is as follows: heating pure nickel, electrolytic copper, copper-manganese alloy and pure zinc to 1250 ℃, preserving heat for 15min after the metal raw materials are completely melted, pouring the metal raw materials into a heat preservation furnace, and carrying out horizontal continuous casting to obtain a casting blank; the casting temperature during the horizontal continuous casting is 1200 ℃;
carrying out surface milling treatment on the casting blank, wherein the upper surface milling amount and the lower surface milling amount are 1 mm;
cogging and blooming the casting blank subjected to surface milling treatment, wherein the total deformation is 80%, and trimming the slab and strip subjected to cogging, wherein the trimming amount is 5mm to obtain the slab and strip;
carrying out bell-type annealing on the plate strip, wherein the annealing temperature is 600 ℃, the heat preservation time is 7h, and the annealing atmosphere comprises 50% by volume of hydrogen and 50% by volume of nitrogen to obtain a first annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the first annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 25%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.15% of benzotriazole water solution, so as to obtain a pickled sheet strip;
carrying out first cold rolling on the pickled plate strip, wherein the temperature of the first cold rolling is 38 ℃, and the total deformation is 80% to obtain a first cold-rolled plate strip;
carrying out bell-type annealing on the first cold-rolled plate strip, wherein the annealing temperature is 600 ℃, the heat preservation time is 7 hours, and the annealing atmosphere is 25% by volume of hydrogen and 75% by volume of nitrogen to obtain a second annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the second annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 20%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so that a second acid-washed sheet strip is obtained;
carrying out second cold rolling on the second acid washing plate strip, wherein the temperature of the second cold rolling is 40 ℃, and the total deformation is 80% to obtain a second cold rolling plate strip;
carrying out bell-type annealing on the second cold-rolled plate strip, wherein the annealing temperature is 580 ℃, the heat preservation time is 6 hours, and the protective gas is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a third annealed plate strip;
and sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the third annealed sheet and strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 10%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.15% of benzotriazole water solution, so that the high-performance zinc white copper is obtained.
The properties of the high performance zinc white copper prepared in this example are shown in table 2.
Example 17
The high-performance zinc white copper of the embodiment is prepared by adopting the following metal raw materials: pure nickel, electrolytic copper, copper-manganese alloy and pure zinc; the chemical composition of the high-performance zinc white copper is shown in table 1.
Smelting by adopting a power frequency induction furnace, wherein the adding sequence of the metal raw materials is as follows: heating pure nickel, electrolytic copper, copper-manganese alloy and pure zinc to 1250 ℃, preserving heat for 15min after the metal raw materials are completely melted, pouring the metal raw materials into a heat preservation furnace, and carrying out horizontal continuous casting to obtain a casting blank; the casting temperature during the horizontal continuous casting is 1200 ℃;
carrying out surface milling treatment on the casting blank, wherein the upper surface milling amount and the lower surface milling amount are 1 mm;
cogging and blooming the casting blank subjected to surface milling treatment, wherein the total deformation is 75%, and trimming the slab and strip subjected to cogging, wherein the trimming amount is 5mm to obtain the slab and strip;
carrying out bell-type annealing on the plate strip, wherein the annealing temperature is 600 ℃, the heat preservation time is 5 hours, and the annealing atmosphere is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a first annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the first annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 25%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.15% of benzotriazole water solution, so as to obtain a pickled sheet strip;
carrying out first cold rolling on the pickled plate strip, wherein the temperature of the first cold rolling is 40 ℃, and the total deformation is 80% to obtain a first cold-rolled plate strip;
carrying out bell-type annealing on the first cold-rolled plate strip, wherein the annealing temperature is 550 ℃, the heat preservation time is 5 hours, and the annealing atmosphere comprises 50% by volume of hydrogen and 50% by volume of nitrogen to obtain a second annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the second annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 20%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so that a second acid-washed sheet strip is obtained;
carrying out second cold rolling on the second acid washing plate strip, wherein the temperature of the second cold rolling is 40 ℃, and the total deformation is 80% to obtain a second cold rolling plate strip;
carrying out bell-type annealing on the second cold-rolled plate strip, wherein the annealing temperature is 540 ℃, the heat preservation time is 8 hours, and the protective gas is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a third annealed plate strip;
and sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the third annealed sheet and strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 8%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.15% of benzotriazole water solution, so that the high-performance zinc white copper is obtained.
The properties of the high performance zinc white copper prepared in this example are shown in table 2.
Example 18
The high-performance zinc white copper of the embodiment is prepared by adopting the following metal raw materials: pure nickel, electrolytic copper, copper-manganese alloy and pure zinc; the chemical composition of the high-performance zinc white copper is shown in table 1.
Smelting by adopting a power frequency induction furnace, wherein the adding sequence of the metal raw materials is as follows: heating pure nickel, electrolytic copper, copper-manganese alloy and pure zinc to 1275 ℃ until the metal raw materials are completely melted, preserving heat for 15min, pouring into a heat preservation furnace, and carrying out horizontal continuous casting to obtain a casting blank; the casting temperature during the horizontal continuous casting is 1150 ℃;
carrying out surface milling treatment on the casting blank, wherein the upper surface milling amount and the lower surface milling amount are 1 mm;
cogging and blooming the casting blank subjected to surface milling treatment, wherein the total deformation is 75%, and trimming the slab and strip subjected to cogging, wherein the trimming amount is 5mm to obtain the slab and strip;
carrying out bell-type annealing on the plate strip, wherein the annealing temperature is 650 ℃, the heat preservation time is 5h, and the annealing atmosphere is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a first annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the first annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 25%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so as to obtain a pickled sheet strip;
carrying out first cold rolling on the pickled plate strip, wherein the temperature of the first cold rolling is 40 ℃, and the total deformation is 80% to obtain a first cold-rolled plate strip;
carrying out bell-type annealing on the first cold-rolled plate strip, wherein the annealing temperature is 550 ℃, the heat preservation time is 8 hours, and the annealing atmosphere comprises 50% by volume of hydrogen and 50% by volume of nitrogen to obtain a second annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the second annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 20%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so that a second acid-washed sheet strip is obtained;
carrying out second cold rolling on the second acid washing plate strip, wherein the temperature of the second cold rolling is 35 ℃, and the total deformation is 80% to obtain a second cold rolling plate strip;
carrying out bell-type annealing on the second cold-rolled plate strip, wherein the annealing temperature is 540 ℃, the heat preservation time is 6 hours, and the protective gas is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a third annealed plate strip;
and sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the third annealed sheet and strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 12%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so that the high-performance zinc white copper is obtained.
The properties of the high performance zinc white copper prepared in this example are shown in table 2.
Example 19
The high-performance zinc white copper of the embodiment is prepared by adopting the following metal raw materials: pure nickel, electrolytic copper, copper-manganese alloy and pure zinc; the chemical composition of the high-performance zinc white copper is shown in table 1.
Smelting by adopting a power frequency induction furnace, wherein the adding sequence of the metal raw materials is as follows: heating pure nickel, electrolytic copper, copper-manganese alloy and pure zinc to 1250 ℃, preserving heat for 15min after the metal raw materials are completely melted, pouring the metal raw materials into a heat preservation furnace, and carrying out horizontal continuous casting to obtain a casting blank; the casting temperature during the horizontal continuous casting is 1175 ℃;
carrying out surface milling treatment on the casting blank, wherein the upper surface milling amount and the lower surface milling amount are 1 mm;
cogging and blooming the casting blank subjected to surface milling treatment, wherein the total deformation is 80%, and trimming the slab and strip subjected to cogging, wherein the trimming amount is 5mm to obtain the slab and strip;
carrying out bell-type annealing on the plate strip, wherein the annealing temperature is 600 ℃, the heat preservation time is 6h, and the annealing atmosphere is 25% by volume of hydrogen and 75% by volume of nitrogen to obtain a first annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the first annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 10%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so as to obtain a pickled sheet strip;
carrying out first cold rolling on the pickled plate strip, wherein the temperature of the first cold rolling is 35 ℃, and the total deformation is 80% to obtain a first cold-rolled plate strip;
carrying out bell-type annealing on the first cold-rolled plate strip, wherein the annealing temperature is 600 ℃, the heat preservation time is 7 hours, and the annealing atmosphere is 25% by volume of hydrogen and 75% by volume of nitrogen to obtain a second annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the second annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 20%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so that a second acid-washed sheet strip is obtained;
carrying out second cold rolling on the second acid washing plate strip, wherein the temperature of the second cold rolling is 40 ℃, and the total deformation is 90%, so as to obtain a second cold rolling plate strip;
carrying out bell-type annealing on the second cold-rolled plate strip, wherein the annealing temperature is 540 ℃, the heat preservation time is 7 hours, and the protective gas is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a third annealed plate strip;
and sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the third annealed sheet and strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 10%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.2% of benzotriazole water solution, so that the high-performance zinc white copper is obtained.
The properties of the high performance zinc white copper prepared in this example are shown in table 2.
Example 20
The high-performance zinc white copper of the embodiment is prepared by adopting the following metal raw materials: pure nickel, electrolytic copper, copper-manganese alloy and pure zinc; the chemical composition of the high-performance zinc white copper is shown in table 1.
Smelting by adopting a power frequency induction furnace, wherein the adding sequence of the metal raw materials is as follows: heating pure nickel, electrolytic copper, copper-manganese alloy and pure zinc to 1275 ℃ until the metal raw materials are completely melted, preserving heat for 15min, pouring into a heat preservation furnace, and carrying out horizontal continuous casting to obtain a casting blank; the casting temperature during the horizontal continuous casting is 1200 ℃;
carrying out surface milling treatment on the casting blank, wherein the upper surface milling amount and the lower surface milling amount are 1 mm;
cogging and blooming the casting blank subjected to surface milling treatment, wherein the total deformation is 80%, and trimming the slab and strip subjected to cogging, wherein the trimming amount is 5mm to obtain the slab and strip;
carrying out bell-type annealing on the plate strip, wherein the annealing temperature is 600 ℃, the heat preservation time is 6h, and the annealing atmosphere comprises 50% by volume of hydrogen and 50% by volume of nitrogen to obtain a first annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the first annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 15%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.2% of benzotriazole water solution, so as to obtain a pickled sheet strip;
carrying out first cold rolling on the pickled plate strip, wherein the temperature of the first cold rolling is 38 ℃, and the total deformation is 80% to obtain a first cold-rolled plate strip;
carrying out bell-type annealing on the first cold-rolled plate strip, wherein the annealing temperature is 550 ℃, the heat preservation time is 7 hours, and the annealing atmosphere is 25% by volume of hydrogen and 75% by volume of nitrogen to obtain a second annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the second annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 20%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so that a second acid-washed sheet strip is obtained;
carrying out second cold rolling on the second acid washing plate strip, wherein the temperature of the second cold rolling is 38 ℃, and the total deformation is 80% to obtain a second cold rolling plate strip;
performing bell-type annealing on the second cold-rolled plate strip, wherein the annealing temperature is 560 ℃, the heat preservation time is 7 hours, and the protective gas is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a third annealed plate strip;
and sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the third annealed sheet and strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 15%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so that the high-performance zinc white copper is obtained.
The properties of the high performance zinc white copper prepared in this example are shown in table 2.
Example 21
The high-performance zinc white copper of the embodiment is prepared by adopting the following metal raw materials: pure nickel, electrolytic copper, copper-manganese alloy and pure zinc; the chemical composition of the high-performance zinc white copper is shown in table 1.
Smelting by adopting a power frequency induction furnace, wherein the adding sequence of the metal raw materials is as follows: heating pure nickel, electrolytic copper, copper-manganese alloy and pure zinc to 1275 ℃ until the metal raw materials are completely melted, preserving heat for 15min, pouring into a heat preservation furnace, and carrying out horizontal continuous casting to obtain a casting blank; the casting temperature during the horizontal continuous casting is 1150 ℃;
carrying out surface milling treatment on the casting blank, wherein the upper surface milling amount and the lower surface milling amount are 1 mm;
cogging and blooming the casting blank subjected to surface milling treatment, wherein the total deformation is 75%, and trimming the slab and strip subjected to cogging, wherein the trimming amount is 5mm to obtain the slab and strip;
carrying out bell-type annealing on the plate strip, wherein the annealing temperature is 600 ℃, the heat preservation time is 5 hours, and the annealing atmosphere is 25% by volume of hydrogen and 75% by volume of nitrogen to obtain a first annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the first annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 25%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so as to obtain a pickled sheet strip;
carrying out first cold rolling on the pickled plate strip, wherein the temperature of the first cold rolling is 38 ℃, and the total deformation is 80% to obtain a first cold-rolled plate strip;
carrying out bell-type annealing on the first cold-rolled plate strip, wherein the annealing temperature is 550 ℃, the heat preservation time is 7 hours, and the annealing atmosphere is 25% by volume of hydrogen and 75% by volume of nitrogen to obtain a second annealed plate strip;
sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the second annealed sheet strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 20%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.1% of benzotriazole water solution, so that a second acid-washed sheet strip is obtained;
carrying out second cold rolling on the second acid washing plate strip, wherein the temperature of the second cold rolling is 40 ℃, and the total deformation is 80% to obtain a second cold rolling plate strip;
carrying out bell-type annealing on the second cold-rolled plate strip, wherein the annealing temperature is 540 ℃, the heat preservation time is 6 hours, and the protective gas is 75% by volume of hydrogen and 25% by volume of nitrogen to obtain a third annealed plate strip;
and sequentially carrying out sulfuric acid washing, water washing and passivating agent washing on the third annealed sheet and strip, wherein the mass concentration of a sulfuric acid solution adopted by the sulfuric acid washing is 12%, and the mass concentration of a passivating agent adopted by the passivating agent washing is 0.15% of benzotriazole water solution, so that the high-performance zinc white copper is obtained.
The properties of the high performance zinc white copper prepared in this example are shown in table 2. In Table 2, the detection standard of tensile strength is GB/T228.1-2010; the detection standard of the hardness is GB/T4340.1-2009; the detection standard of the glossiness is GB/T9754-2007; the detection standard of the roughness is GB/T10610-2009; the detection standard of the grain size is YS/T347-2004.
TABLE 1 chemical composition (wt%) of high performance zinc white copper of examples 1 to 21
Figure BDA0003105755360000281
Figure BDA0003105755360000291
TABLE 2 Properties of high Performance Zinc white copper for examples 1-21
Figure BDA0003105755360000292
Figure BDA0003105755360000301
As can be seen from Table 2, the high-performance copper-nickel alloy provided by the invention has the advantages of high strength, high hardness, high glossiness, low roughness and low grain size, and can meet the requirements of various industrial fields on the copper-nickel alloy material.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The high-performance zinc white copper is characterized by comprising the following chemical components in percentage by mass: 16.5-19.5% of nickel, 12-20% of zinc, 0.1-0.25% of iron, 0.2-0.5% of manganese, 0-0.05% of lead and the balance of copper.
2. The high-performance zinc white copper according to claim 1, characterized in that the chemical composition comprises, in mass percent: 17.25-18.75% of nickel, 14-18% of zinc, 0.137-0.213% of iron, 0.275-0.425% of manganese, 0.013-0.038% of lead and the balance of copper.
3. The method for preparing the high-performance zinc white copper as claimed in any one of claims 1 to 2, which comprises the following steps:
smelting and casting a metal raw material to obtain a casting blank; the chemical components of the metal raw material are consistent with those of the high-performance zinc white copper in any one of claims 1-2;
cogging and blooming the casting blank to obtain a plate and strip;
carrying out first annealing on the plate strip to obtain a first annealed plate strip;
carrying out first cold rolling on the first annealing plate strip to obtain a first cold-rolled plate strip;
carrying out second annealing on the first cold-rolled plate strip to obtain a second annealed plate strip;
carrying out second cold rolling on the second annealing plate strip to obtain a second cold-rolled plate strip;
and carrying out third annealing on the second cold-rolled plate strip to obtain the high-performance zinc white copper.
4. The preparation method according to claim 3, wherein the temperature of the smelting is 1250-1300 ℃; the casting temperature is 1150-1200 ℃.
5. The production method according to claim 3, wherein the total deformation amount of the cogging blooming is 75 to 80%.
6. The preparation method according to claim 3, wherein the temperature of the first annealing is 600-700 ℃ and the holding time is 5-7 h.
7. The method of claim 3, wherein the first cold rolling has a total deformation amount of 70 to 80%.
8. The preparation method according to claim 3, wherein the temperature of the second annealing is 550-600 ℃, and the holding time is 6-8 h.
9. The method of claim 3, wherein the second cold rolling has a total deformation amount of 60 to 90%.
10. The preparation method of claim 3, wherein the temperature of the third annealing is 540-580 ℃, and the holding time is 6-8 h.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1690236A (en) * 2004-04-20 2005-11-02 上海金泰铜业有限公司 Nickel silver band for piezoelectric crystal oscillator housing and method for producing same
CN102758100A (en) * 2012-07-18 2012-10-31 宁波兴业盛泰集团有限公司 High-strength high-elasticity zinc-copper-nickel alloy and processing method thereof
CN107151750A (en) * 2017-05-22 2017-09-12 宁波博威合金板带有限公司 A kind of nickel silver alloy and its preparation method and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1690236A (en) * 2004-04-20 2005-11-02 上海金泰铜业有限公司 Nickel silver band for piezoelectric crystal oscillator housing and method for producing same
CN102758100A (en) * 2012-07-18 2012-10-31 宁波兴业盛泰集团有限公司 High-strength high-elasticity zinc-copper-nickel alloy and processing method thereof
CN107151750A (en) * 2017-05-22 2017-09-12 宁波博威合金板带有限公司 A kind of nickel silver alloy and its preparation method and application

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