CN115354163B - Preparation method of fine-grain high-purity oxygen-free copper plate - Google Patents

Preparation method of fine-grain high-purity oxygen-free copper plate Download PDF

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CN115354163B
CN115354163B CN202210836303.1A CN202210836303A CN115354163B CN 115354163 B CN115354163 B CN 115354163B CN 202210836303 A CN202210836303 A CN 202210836303A CN 115354163 B CN115354163 B CN 115354163B
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oxygen
smelting
copper plate
crystallizer
furnace
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CN115354163A (en
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王群
梁相博
孙君鹏
王杰飞
周斌
刘琦
刘向东
王朝阳
王文斌
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Sirui Advanced Copper Alloy Co ltd
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Sirui Advanced Copper Alloy Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/16—Remelting metals
    • C22B9/22—Remelting metals with heating by wave energy or particle radiation
    • C22B9/228—Remelting metals with heating by wave energy or particle radiation by particle radiation, e.g. electron beams
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0026—Pyrometallurgy
    • C22B15/006—Pyrometallurgy working up of molten copper, e.g. refining
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/05—Refining by treating with gases, e.g. gas flushing also refining by means of a material generating gas in situ
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
    • 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
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention provides a preparation method of a fine-grain high-purity oxygen-free copper plate, and belongs to the technical field of copper alloy preparation. The method comprises the following steps: s1, charging; s2, electron beam cold bed smelting; s3, hot-pressing blank making; s4, hot rolling; s5, milling the surface; s6, cold rolling; s7, stress relief annealing; the invention adopts electron beam cold bed smelting to remove impurities in electrolytic copper, and the power of each smelting area is set according to the technological requirement, so that the purity of the prepared oxygen-free copper plate can reach more than 99.995%, the oxygen content is less than 5ppm, the grain size of the plate is less than 70um, and the structure is compact without pores, impurities and shrinkage porosity; oxygen absorption characteristics of oxygen absorption composite modified graphene are utilized to absorb oxygen contacted with the surface of copper liquid during smelting, and meanwhile, the oxygen in the container can be further removed by the method of combining composite mixed gas degassing, so that the effect of isolating the copper liquid from the oxygen is achieved, and the purity and heat resistance of the oxygen-free copper plate are improved.

Description

Preparation method of fine-grain high-purity oxygen-free copper plate
Technical Field
The invention belongs to the technical field of copper alloy preparation, and particularly relates to a preparation method of a fine-grain high-purity oxygen-free copper plate.
Background
With the development of high and new technology and the demand of strategic materials, the requirement of high-purity metal on purity is higher and higher, and the preparation and application of high-purity copper are in a growing trend in the modern material science and engineering fields. Therefore, oxygen-free copper with high purity and low oxygen content needs to be developed to meet the product and market demands.
The high-purity oxygen-free copper has good conductivity, ductility and corrosion resistance, and is widely applied to various connecting wires in the electronic industry, electronic packaging bonding wires, high-quality audio wires, vacuum electronic devices, superconductivity, medical treatment and integrated circuits, sputtering targets of liquid crystal displays, ion plating films and other high and new technical fields.
The current production process of the oxygen-free copper plate mainly comprises a non-vacuum smelting and rolling method for producing the oxygen-free copper, wherein the oxygen-free copper is produced by adopting an open type induction smelting method, firstly, the hydrogen content in the copper liquid is reduced by adopting oxidation degassing, and then the oxygen content in the copper liquid is reduced by deoxidization refining.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of a fine-grain high-purity oxygen-free copper plate with high purity and extremely low oxygen content and impurity content.
The technical scheme of the invention is as follows: the preparation method of the fine-grain high-purity oxygen-free copper plate comprises the following steps:
s1, charging
Firstly, cleaning a hearth of an electron beam cold bed smelting furnace, cutting an electrolytic copper plate into a specification of 1000 multiplied by 370 multiplied by 15, putting the electrolytic copper plate into a horizontal feeder in a feed bin, cleaning an observation window, covering a furnace cover, and vacuumizing;
s2, electron beam cold bed smelting
When the vacuum degree in the electron beam cold hearth furnace reaches 1 multiplied by 10 -2 When torr, starting an electron gun to start melting, enabling a melt to flow into a crystallizer through a cooling bed, and starting to pull down when copper liquid flows into the crystallizer through the cooling bed and completely covers a crystallizer pull head;
s3, hot-pressing blank making
Heating by using a gas furnace at 750-780 ℃, preserving heat for 4-5h, forging and pressing on a 3150 ton oil press to enable the final forging temperature to be higher than 500 ℃, wherein the cross section size of the blank is 605 multiplied by 100;
s4, hot rolling
Heating by using a gas furnace, keeping the temperature at 750-780 ℃ for 3-4 hours, and then carrying out hot rolling on a two-roll reversible rolling mill in a split way to ensure that the total rolling reduction is 60-85%;
s5, milling surface
Milling the hot rolled and cogged plate material up and down on double-sided milling equipment, wherein the milling thickness is 1mm, so as to remove oxide skin on the surface of the hot rolled blank material;
s6, cold rolling
Carrying out split-pass cold rolling on the medium plate on a four-roller reversible rolling mill, wherein the total deformation of the cold rolling is more than 40%;
s7, stress relief annealing
And (3) annealing the semi-finished plate for 1h, controlling the temperature to be 250-280 ℃, carrying out surface cleaning after annealing treatment to obtain a finished plate, and finally cutting according to the external dimension of the product.
Further, in the step S2, electron beam cold bed melting is divided into the following four stages;
s2-1, stage of starting the electron gunThe copper liquid flows into the crystallizer for the first time after being melted, and the vacuum degree in the furnace is 8.2 multiplied by 10 -3 torr, time 65min;
s2-2, in the bottom making stage of the ingot, from the first time of copper liquid flowing into the crystallizer to the beginning of ingot pulling down, the vacuum degree in the furnace is 7.0 multiplied by 10 -3 torr, time is 35min;
s2-3, in the normal smelting stage, from the first pulling-down of the cast ingot to the beginning of the reduction of smelting speed and smelting power, the vacuum degree in the furnace is 4.0 multiplied by 10 -3 torr, time is 120min, and average smelting speed is 350kg/h;
s2-4, the smelting finishing stage, from the beginning of smelting power and smelting speed to the end of smelting ingot casting, the time is 15min, and the vacuum degree is 2.4X10 -3 torr。
Further, in the step S2, the 1# electron gun is used for melting the copper plate, the current is 6-9A, the power of the melting area is set to be 210-240KW, the 2# electron gun is used for the crystallizer, the surface of a molten pool in the crystallizer is completely melted, the current is 2-4A, the power of the melting area is 80-100KW, the 3# electron gun is used for the cold bed refining area, the copper liquid flows into the crystallizer from the cold bed through the sprue gate, the current is 1-3A, the power of the melting area is 50-70KW, and the smelting effect is improved by respectively controlling the powers of different melting areas.
Further, in the step S1, before cutting the electrolytic copper plate, the mixed water jet method is adopted to remove the surface oxide layer of the electrolytic copper plate, then the electrolytic copper plate is placed in a muffle reduction furnace, and is subjected to vacuum heating anaerobic treatment for 1-2 hours at the temperature of 350-400 ℃, the mixed water jet method is a pure physical method, the oxide layer on the surface of the electrolytic copper plate is removed in the removing mode by the method, the original performance of the electrolytic copper plate is not damaged, the oxidation of a workpiece can be avoided by the vacuum heating anaerobic treatment, so that the oxygen content is reduced, and the purity and the performance of the oxygen-free copper plate are improved.
Further, in the step S2, after the copper liquid flows into the crystallizer through the cooling bed, oxygen-absorbing composite modified graphene is added into the copper liquid as an oxygen barrier layer, then, a composite mixed gas degassing method is adopted, mixed gas is injected into the crystallizer to prevent oxidation of the surface of the copper liquid, oxygen contacted with the surface of the copper liquid is adsorbed by utilizing the oxygen absorbing characteristic of the oxygen-absorbing composite modified graphene, and meanwhile, oxygen in the container can be further removed by adopting the composite mixed gas degassing method, so that the effect of isolating the copper liquid from the oxygen is achieved, the purity and the heat resistance of the oxygen-free copper plate are improved, compared with the pure physical method of inert gas for degassing, the composite mixed gas for degassing has physical degassing and chemical degassing, and the degassing effect is more outstanding.
Further, the mixed gas is N 2 And C 2 H 2 Mixing at a volume ratio of 2:1, wherein the gas mixture is introduced in an amount of 0.5-0.6L/min.
Further, the preparation method of the oxygen uptake composite modified graphene comprises the following steps:
(1) Mixing graphite, sodium metanitrobenzenesulfonate, acrylic acid and concentrated sulfuric acid with the concentration of 98% according to the mass ratio of 1:2:8:25, adding the mixture into a reaction kettle, reacting for 1-2 hours at the temperature of 25-30 ℃ to obtain a mixed solution, adding potassium dichromate into the mixed solution, and stirring for 20-30 minutes by adopting an electromagnetic suspension stirring method to obtain a solution I, wherein the mass ratio of the graphite to the potassium dichromate is 1:6;
(2) Adding 25% hydrogen peroxide by weight into the solution I, uniformly stirring, filtering, and washing filter residues to be neutral to obtain graphene oxide;
(3) According to the mass ratio of 1:1:5, graphene oxide and 3, 4-epoxy-1-butene are dissolved in an ethanol solution with the concentration of 68%, an electromagnetic suspension stirring method is adopted to stir for 15-20min, a solution II is obtained, and after refluxing, washing, suction filtration and drying, oxygen-absorbing composite modified graphene is obtained, oxygen contacted with the surface of a copper liquid is absorbed through the oxygen absorbing characteristic of the prepared oxygen-absorbing composite modified graphene, so that the effect of isolating the copper liquid from the oxygen is achieved, and the purity and the heat resistance of the oxygen-free copper plate are improved.
Further, in the step S2, when the copper liquid flows into the crystallizer through the cooling bed and completely covers the crystallizer drawing head, the drawing is started, and the drawing speed is 300-360kg/h.
Further, in the step S7, the stress relief annealing process is as follows: firstly, pickling a finished product of oxygen-free copper plate by using a hydrochloric acid solution with the concentration of 28-30%, washing and drying, then, putting the pickled finished product of oxygen-free copper plate into an annealing device, filling nitrogen into the annealing device, carrying out annealing treatment at the heating rate of 5-6 ℃/min until the temperature reaches 250-280 ℃, and finally cooling to room temperature.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention adopts the means of electron beam cold bed smelting, hot forging, hot rolling, face milling, cold rolling, annealing treatment and the like to remove impurities in electrolytic copper, and the power of each smelting area is set according to the technological requirements, so that the purity of the prepared oxygen-free copper plate can reach more than 99.995 percent, the oxygen content is less than 5ppm, the grain size of the plate is less than 70um, the structure is compact, and no air holes, impurities and shrinkage porosity are found.
(2) According to the oxygen-absorbing composite modified graphene, oxygen contacted with the surface of the copper liquid during smelting is absorbed by utilizing the oxygen-absorbing characteristic of the oxygen-absorbing composite modified graphene, and meanwhile, the oxygen in the container can be further removed by adopting the method of degassing by the composite mixed gas, so that the effect of isolating the copper liquid from the oxygen is achieved, and the purity and the heat resistance of the oxygen-free copper plate are improved.
Drawings
FIG. 1 is a main flow chart of the process of preparing an oxygen-free copper plate according to the present invention;
FIG. 2 is a golden phase diagram of an oxygen free copper ingot of the present invention;
FIG. 3 is a golden phase diagram of an oxygen free copper plate of the present invention.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
As shown in FIG. 1, the preparation method of the fine-grain high-purity oxygen-free copper plate comprises the following steps:
s1, charging
Firstly, cleaning a hearth of an electron beam cold bed smelting furnace, cutting an electrolytic copper plate into a specification of 1000 multiplied by 370 multiplied by 15, putting the electrolytic copper plate into a horizontal feeder in a feed bin, cleaning an observation window, covering a furnace cover, and vacuumizing;
s2, electron beam cold bed smelting
When the vacuum degree in the electron beam cold hearth furnace reaches 1 multiplied by 10 -2 When torr, an electron gun is started to start melting, a melt flows into a crystallizer through a cooling bed, when copper liquid flows into the crystallizer through the cooling bed and completely covers a crystallizer pull head, the pull-down speed is 300kg/h, and smelting is divided into the following four stages:
s2-1, starting an electron gun stage, wherein the molten copper flows into a crystallizer for the first time after being melted, and the vacuum degree in the furnace is 8.2 multiplied by 10 -3 torr, time 65min;
s2-2, in the bottom making stage of the ingot, from the first time of copper liquid flowing into the crystallizer to the beginning of ingot pulling down, the vacuum degree in the furnace is 7.0 multiplied by 10 -3 torr, time is 35min;
s2-3, in the normal smelting stage, from the first pulling-down of the cast ingot to the beginning of the reduction of smelting speed and smelting power, the vacuum degree in the furnace is 4.0 multiplied by 10 -3 torr, time is 120min, and average smelting speed is 350kg/h;
s2-4, the smelting finishing stage, from the beginning of smelting power and smelting speed to the end of smelting ingot casting, the time is 15min, and the vacuum degree is 2.4X10 -3 torr；
In the process, the No. 1 electron gun is used for melting the copper plate, the current is 6-9A, the power of a melting area is set to be 210KW, the No. 2 electron gun is used for a crystallizer, the surface of a molten pool in the crystallizer is completely melted, the current is 2A, the power of the melting area is 80KW, the No. 3 electron gun is used for a cooling bed refining area, copper liquid flows into the crystallizer from a cooling bed through a pouring gate, the current is 1A, and the power of the melting area is 50KW.
S3, hot-pressing blank making
Heating by using a gas furnace, wherein the heating temperature is 750 ℃, preserving heat for 4 hours, forging and pressing on a 3150 ton oil press to enable the final forging temperature to be more than 500 ℃, and the cross section size of the blank is 605 multiplied by 100;
s4, hot rolling
Heating by using a gas furnace, keeping the temperature at 750 ℃, and carrying out hot rolling on a two-roll reversible rolling mill in a split way after preserving heat for 3 hours, so that the total rolling reduction is 60%;
s5, milling surface
Milling the hot rolled and cogged plate material up and down on double-sided milling equipment, wherein the milling thickness is 1mm, so as to remove oxide skin on the surface of the hot rolled blank material;
s6, cold rolling
Carrying out split-pass cold rolling on the medium plate on a four-roller reversible rolling mill, wherein the total deformation of the cold rolling is more than 40%;
s7, stress relief annealing
And (3) carrying out annealing treatment on the semi-finished plate for 1h, controlling the temperature at 250 ℃, carrying out surface cleaning after the annealing treatment to obtain a finished plate, and finally cutting according to the outline dimension of the product.
Example 2
As shown in FIG. 1, the preparation method of the fine-grain high-purity oxygen-free copper plate comprises the following steps:
s1, charging
Firstly, cleaning a hearth of an electron beam cold bed smelting furnace, cutting an electrolytic copper plate into a specification of 1000 multiplied by 370 multiplied by 15, putting the electrolytic copper plate into a horizontal feeder in a feed bin, cleaning an observation window, covering a furnace cover, and vacuumizing;
s2, electron beam cold bed smelting
When the vacuum degree in the electron beam cold hearth furnace reaches 1 multiplied by 10 -2 When torr, an electron gun is started to start melting, a melt flows into a crystallizer through a cooling bed, when copper liquid flows into the crystallizer through the cooling bed and completely covers a crystallizer pull head, the pull-down speed is 330kg/h, and the melting is divided into the following four stages:
s2-1, starting an electron gun stage, wherein the molten copper flows into a crystallizer for the first time after being melted, and the vacuum degree in the furnace is 8.2 multiplied by 10 -3 torr, time 65min;
s2-2, in the bottom making stage of the ingot, from the first time of copper liquid flowing into the crystallizer to the beginning of ingot pulling down, the vacuum degree in the furnace is 7.0 multiplied by 10 -3 torr, time is 35min;
s2-3, in the normal smelting stage, from the first pulling-down of the cast ingot to the beginning of the reduction of smelting speed and smelting power, the vacuum degree in the furnace is 4.0 multiplied by 10 -3 torr, time is 120min, and average smelting speed is 350kg/h;
s2-4, the smelting finishing stage, from the beginning of smelting power and smelting speed to the end of smelting ingot casting, the time is 15min, and the vacuum degree is 2.4X10 -3 torr；
In the process, the 1# electron gun is used for melting the copper plate, the current is 8A, the power of a melting area is set to 220KW, the 2# electron gun is used for a crystallizer, the surface of a molten pool in the crystallizer is completely melted, the current is 3A, the power of the melting area is 90KW, the 3# electron gun is used for a cold bed refining area, copper liquid flows into the crystallizer from a cold bed through a pouring gate, the current is 2A, and the power of the melting area is 60KW.
S3, hot-pressing blank making
Heating by using a gas furnace at 765 ℃, preserving heat for 4-5h, forging and pressing on a 3150 ton oil press to enable the final forging temperature to be higher than 500 ℃, wherein the cross section size of the blank is 605 multiplied by 100;
s4, hot rolling
Heating by using a gas furnace, keeping the temperature at 770 ℃, and carrying out hot rolling on a two-roll reversible rolling mill in batches after preserving the heat for 3.5 hours to ensure that the total rolling reduction is 75%;
s5, milling surface
Milling the hot rolled and cogged plate material up and down on double-sided milling equipment, wherein the milling thickness is 1mm, so as to remove oxide skin on the surface of the hot rolled blank material;
s6, cold rolling
Carrying out split-pass cold rolling on the medium plate on a four-roller reversible rolling mill, wherein the total deformation of the cold rolling is more than 40%;
s7, stress relief annealing
And (3) carrying out annealing treatment on the semi-finished plate for 1h, controlling the temperature at 270 ℃, carrying out surface cleaning after the annealing treatment to obtain a finished plate, and finally cutting according to the outline dimension of the product.
Example 3
As shown in FIG. 1, the preparation method of the fine-grain high-purity oxygen-free copper plate comprises the following steps:
s1, charging
Firstly, cleaning a hearth of an electron beam cold bed smelting furnace, cutting an electrolytic copper plate into a specification of 1000 multiplied by 370 multiplied by 15, putting the electrolytic copper plate into a horizontal feeder in a feed bin, cleaning an observation window, covering a furnace cover, and vacuumizing;
s2, electron beam cold bed smelting
When the vacuum degree in the electron beam cold hearth furnace reaches 1 multiplied by 10 -2 When torr, an electron gun is started to start melting, a melt flows into a crystallizer through a cooling bed, when copper liquid flows into the crystallizer through the cooling bed and completely covers a crystallizer pull head, the pull-down speed is 360kg/h, and the melting is divided into the following four stages:
s2-1, starting an electron gun stage, wherein the molten copper flows into a crystallizer for the first time after being melted, and the vacuum degree in the furnace is 8.2 multiplied by 10 -3 torr, time 65min;
s2-2, in the bottom making stage of the ingot, from the first time of copper liquid flowing into the crystallizer to the beginning of ingot pulling down, the vacuum degree in the furnace is 7.0 multiplied by 10 -3 torr, time is 35min;
s2-3, in the normal smelting stage, from the first pulling-down of the cast ingot to the beginning of the reduction of smelting speed and smelting power, the vacuum degree in the furnace is 4.0 multiplied by 10 -3 torr, time is 120min, and average smelting speed is 350kg/h;
s2-4, the smelting finishing stage, from the beginning of smelting power and smelting speed to the end of smelting ingot casting, the time is 15min, and the vacuum degree is 2.4X10 -3 torr；
In the process, the 1# electron gun is used for melting the copper plate, the current is 9A, the power of a melting area is set to 240KW, the 2# electron gun is used for a crystallizer, the surface of a molten pool in the crystallizer is completely melted, the current is 4A, the power of the melting area is 100KW, the 3# electron gun is used for a cold bed refining area, copper liquid flows into the crystallizer from a cold bed through a pouring gate, the current is 3A, and the power of the melting area is 70KW.
S3, hot-pressing blank making
Heating by using a gas furnace, wherein the heating temperature is 780 ℃, preserving heat for 5 hours, forging and pressing on a 3150 ton oil press to ensure that the final forging temperature is more than 500 ℃, and the cross section size of the blank is 605 multiplied by 100;
s4, hot rolling
Heating by using a gas furnace, keeping the temperature at 780 ℃ for 4 hours, and then carrying out hot rolling on a two-roll reversible rolling mill in a split way to ensure that the total rolling reduction is 85%;
s5, milling surface
Milling the hot rolled and cogged plate material up and down on double-sided milling equipment, wherein the milling thickness is 1mm, so as to remove oxide skin on the surface of the hot rolled blank material;
s6, cold rolling
Carrying out split-pass cold rolling on the medium plate on a four-roller reversible rolling mill, wherein the total deformation of the cold rolling is more than 40%;
s7, stress relief annealing
And (3) carrying out annealing treatment on the semi-finished plate for 1h, controlling the temperature at 280 ℃, carrying out surface cleaning after the annealing treatment to obtain a finished plate, and finally cutting according to the outline dimension of the product.
Example 4
This embodiment is substantially the same as embodiment 3 except that:
in the step S1, before cutting the electrolytic copper plate, firstly adopting a mixed water jet method to remove an oxidation layer on the outer surface of the electrolytic copper plate, then placing the electrolytic copper plate into a muffle reduction furnace, and carrying out vacuum heating anaerobic treatment for 1.5h at the temperature of 380 ℃.
Example 5
This embodiment is substantially the same as embodiment 3 except that:
in step S2, after copper liquid flows into the crystallizer through the cooling bed, oxygen-absorbing composite modified graphene is added into the copper liquid as an oxygen barrier layer, and then mixed gas is injected into the crystallizer by adopting a composite mixed gas degassing method to prevent the surface of the copper liquid from being oxidized, wherein the mixed gas is N 2 And C 2 H 2 Mixing according to the volume ratio of 2:1, wherein the ventilation amount of the mixed gas is 0.55L/min;
the preparation method of the oxygen absorption composite modified graphene comprises the following steps:
(1) Mixing graphite, sodium metanitrobenzenesulfonate, acrylic acid and concentrated sulfuric acid with the concentration of 98% according to the mass ratio of 1:2:8:25, adding the mixture into a reaction kettle, reacting for 1.5 hours at the temperature of 28 ℃ to obtain a mixed solution, adding potassium dichromate into the mixed solution, and stirring for 25 minutes by adopting an electromagnetic suspension stirring method to obtain a solution I, wherein the mass ratio of the graphite to the potassium dichromate is 1:6;
(2) Adding 25% hydrogen peroxide by weight into the solution I, uniformly stirring, filtering, and washing filter residues to be neutral to obtain graphene oxide;
(3) According to the mass ratio of 1:1:5, graphene oxide and 3, 4-epoxy-1-butene are dissolved in an ethanol solution with the concentration of 68%, an electromagnetic suspension stirring method is adopted for stirring for 18min, a solution II is obtained, and then the oxygen absorption composite modified graphene is obtained after reflux, washing, suction filtration and drying.
Example 6
This embodiment is substantially the same as embodiment 3 except that:
in step S7, the stress relief annealing process is as follows: firstly, pickling a finished product of oxygen-free copper plate by using a hydrochloric acid solution with the concentration of 30%, washing and drying, then, putting the pickled finished product of oxygen-free copper plate into an annealing device, filling nitrogen into the annealing device, carrying out annealing treatment at the heating rate of 6 ℃/min until the temperature reaches 280 ℃, and finally, cooling to the room temperature.
Test examples
The oxygen-free copper sheets prepared by the methods of examples 1 to 6 were each examined for copper chemical composition/gas content by using an examination apparatus, and specific examination results are shown in tables 1 and 2:
table 1: copper chemical composition detection Table of oxygen-free copper plate prepared by the method of examples 1 to 6
Table 2: gas content detection Table of oxygen-free copper plate prepared by the method of examples 1 to 6
Element(s) Content ppm wt
H ＜3
C ＜3
N ＜3
O 2
As is clear from Table 1, the oxygen-free copper sheets prepared in examples 1 to 6 were low in various chemical impurities and gas contents, and were stable to 99.995% or more, and the oxygen content was less than 5ppm, and as shown in FIGS. 2 and 3, the oxygen-free copper sheets were dense in structure and free from voids, inclusions and shrinkage porosity, and therefore, the oxygen-free copper sheets prepared in examples 1 to 6 were fine-grained high-purity oxygen-free copper sheets having high purity, low oxygen content and small grain size.

Claims (4)

1. The preparation method of the fine-grain high-purity oxygen-free copper plate is characterized by comprising the following steps of:
s1, charging
Firstly, cleaning a hearth of an electron beam cold bed smelting furnace, cutting an electrolytic copper plate into a specification of 1000 multiplied by 370 multiplied by 15, putting the electrolytic copper plate into a horizontal feeder in a feed bin, cleaning an observation window, covering a furnace cover, and vacuumizing;
s2, electron beam cold bed smelting
When the vacuum degree in the electron beam cold hearth furnace reaches 1 multiplied by 10 -2 When torr, starting an electron gun to start melting, enabling a melt to flow into a crystallizer through a cooling bed, and starting to pull down when copper liquid flows into the crystallizer through the cooling bed and completely covers a crystallizer pull head;
s3, hot-pressing blank making
Heating by using a gas furnace at 750-780 ℃, preserving heat for 4-5h, forging and pressing on a 3150 ton oil press to enable the final forging temperature to be higher than 500 ℃, wherein the cross section size of the blank is 605 multiplied by 100;
s4, hot rolling
Heating by using a gas furnace, keeping the temperature at 750-780 ℃ for 3-4 hours, and then carrying out hot rolling on a two-roll reversible rolling mill in a split way to ensure that the total rolling reduction is 60-85%;
s5, milling surface
Milling the hot rolled and cogged plate material up and down on double-sided milling equipment, wherein the milling thickness is 1mm, so as to remove oxide skin on the surface of the hot rolled blank material;
s6, cold rolling
Carrying out split cold rolling on the medium plate on a four-roller reversible rolling mill, wherein the total deformation of the cold rolling is more than 40%;
s7, stress relief annealing
Annealing the semi-finished plate for 1h, controlling the temperature to be 250-280 ℃, cleaning the surface after annealing to obtain a finished plate, and finally cutting according to the external dimension of the product;
in the step S2, after copper liquid flows into a crystallizer through a cooling bed, oxygen-absorbing composite modified graphene is added into the copper liquid to serve as an oxygen barrier layer, and then, a composite mixed gas degassing method is adopted, and mixed gas is injected into the crystallizer to prevent the surface of the copper liquid from being oxidized;
the mixed gas is N 2 And C 2 H 2 Mixing according to the volume ratio of 2:1, wherein the ventilation amount of the mixed gas is 0.5-0.6L/min;
the preparation method of the oxygen absorption composite modified graphene comprises the following steps:
(1) Mixing graphite, sodium metanitrobenzenesulfonate, acrylic acid and concentrated sulfuric acid with the concentration of 98% according to the mass ratio of 1:2:8:25, adding the mixture into a reaction kettle, reacting for 1-2 hours at the temperature of 25-30 ℃ to obtain a mixed solution, adding potassium dichromate into the mixed solution, and stirring for 20-30 minutes by adopting an electromagnetic suspension stirring method to obtain a solution I, wherein the mass ratio of the graphite to the potassium dichromate is 1:6;
(2) Adding 25% hydrogen peroxide by weight into the solution I, uniformly stirring, filtering, and washing filter residues to be neutral to obtain graphene oxide;
(3) According to the mass ratio of 1:1:5, graphene oxide and 3, 4-epoxy-1-butene are dissolved in an ethanol solution with the concentration of 68%, an electromagnetic suspension stirring method is adopted for stirring for 15-20min to obtain a solution II, and then the oxygen absorption composite modified graphene is obtained after reflux, washing, suction filtration and drying;
in the step S2, electron beam cold bed smelting is divided into the following four stages;
s2-1, starting an electron gun stage, wherein the molten copper flows into a crystallizer for the first time after being melted, and the vacuum degree in the furnace is 8.2 multiplied by 10 - 3 torr, time 65min;
s2-2, in the bottom making stage of the ingot, from the first time of copper liquid flowing into the crystallizer to the beginning of ingot pulling down, the vacuum degree in the furnace is 7.0 multiplied by 10 - 3 torr, time is 35min;
s2-3, in the normal smelting stage, from the first pulling-down of the cast ingot to the beginning of the reduction of smelting speed and smelting power, the vacuum degree in the furnace is 4.0 multiplied by 10 -3 torr, time is 120min, and average smelting speed is 350kg/h;
s2-4, the smelting finishing stage, from the beginning of smelting power and smelting speed to the end of smelting ingot casting, the time is 15min, and the vacuum degree is 2.4X10 -3 torr；
In the step S2, the 1# electron gun is used for melting a copper plate, the current is 6-9A, the power of a melting area is set to be 210-240KW, the 2# electron gun is used for a crystallizer, the surface of a molten pool in the crystallizer is completely melted, the current is 2-4A, the power of the melting area is 80-100KW, the 3# electron gun is used for a cold bed refining area, copper liquid flows into the crystallizer from the cold bed through a sprue gate, the current is 1-3A, and the power of the melting area is 50-70KW.
2. The method for preparing the fine-grain high-purity oxygen-free copper plate according to claim 1, wherein in the step S1, before cutting the electrolytic copper plate, a mixed water jet method is adopted to remove an oxide layer on the outer surface of the electrolytic copper plate, and then the electrolytic copper plate is placed into a muffle reduction furnace to be subjected to vacuum heating and oxygen-free treatment for 1-2 hours at the temperature of 350-400 ℃.
3. The method for producing a fine-grain high-purity oxygen-free copper sheet according to claim 1, wherein in the step S2, the drawing is started when the copper liquid flows into the mold through the cooling bed and completely covers the mold drawing head, and the drawing speed is 300 to 360kg/h.
4. The method for preparing a fine-grain high-purity oxygen-free copper plate according to claim 1, wherein in the step S7, the stress relief annealing process is as follows: firstly, pickling a finished product of oxygen-free copper plate by using a hydrochloric acid solution with the concentration of 28-30%, washing and drying, then, putting the pickled finished product of oxygen-free copper plate into an annealing device, filling nitrogen into the annealing device, carrying out annealing treatment at the heating rate of 5-6 ℃/min until the temperature reaches 250-280 ℃, and finally cooling to the room temperature.
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