CN114657492A - Method for preparing oxygen-free copper rod by dip coating and oxygen-free copper rod prepared by method - Google Patents
Method for preparing oxygen-free copper rod by dip coating and oxygen-free copper rod prepared by method Download PDFInfo
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- CN114657492A CN114657492A CN202210225555.0A CN202210225555A CN114657492A CN 114657492 A CN114657492 A CN 114657492A CN 202210225555 A CN202210225555 A CN 202210225555A CN 114657492 A CN114657492 A CN 114657492A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 233
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 231
- 239000010949 copper Substances 0.000 title claims abstract description 231
- 238000003618 dip coating Methods 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 64
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000001301 oxygen Substances 0.000 claims abstract description 87
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 87
- 239000007788 liquid Substances 0.000 claims abstract description 74
- 230000001681 protective effect Effects 0.000 claims abstract description 30
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000005098 hot rolling Methods 0.000 claims abstract description 6
- 238000005266 casting Methods 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 57
- 229910002804 graphite Inorganic materials 0.000 claims description 57
- 239000010439 graphite Substances 0.000 claims description 57
- 239000003610 charcoal Substances 0.000 claims description 42
- 239000011248 coating agent Substances 0.000 claims description 40
- 238000000576 coating method Methods 0.000 claims description 40
- 238000002844 melting Methods 0.000 claims description 26
- 230000008018 melting Effects 0.000 claims description 26
- 238000004519 manufacturing process Methods 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 16
- 238000004140 cleaning Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- 239000002893 slag Substances 0.000 claims description 14
- 238000002485 combustion reaction Methods 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000003345 natural gas Substances 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 7
- 238000007667 floating Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 57
- 238000003466 welding Methods 0.000 description 53
- 239000007789 gas Substances 0.000 description 20
- 239000012535 impurity Substances 0.000 description 14
- 230000002829 reductive effect Effects 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000001514 detection method Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000004321 preservation Methods 0.000 description 9
- 238000012545 processing Methods 0.000 description 8
- 238000007873 sieving Methods 0.000 description 8
- 239000000779 smoke Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000004364 calculation method Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- -1 and at the moment Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 238000012886 linear function Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Coating With Molten Metal (AREA)
Abstract
The invention belongs to the field of metallurgy, and particularly relates to a method for preparing an oxygen-free copper rod by dip coating. The method comprises the following steps: carrying out dip-coating treatment on the pretreated oxygen-free copper female rod by passing through molten copper dip-coating liquid, controlling the temperature and the dip-coating time of the copper dip-coating liquid in a closed container to ensure that the surface of the oxygen-free copper female rod absorbs heat and softens, then carrying out traction on the oxygen-free copper female rod after adsorbing the copper dip-coating liquid to form a copper cast rod, and carrying out post-treatment on the copper cast rod to obtain the oxygen-free copper rod; the pretreatment comprises descaling; the post-treatment comprises cooling, hot rolling and re-cooling in sequence; the copper dip coating liquid, the copper casting rod and the post-treatment are protected by a reducing protective atmosphere; the temperature of the copper dip-coating solution is 1220-1250 ℃, and the dip-coating time is 0.5-1.3 s. The invention can reduce the oxygen content of the oxygen-free copper rod and meet the market demand of high-quality oxygen-free copper rods.
Description
Technical Field
The invention belongs to the field of metallurgy, and particularly relates to a method for preparing an oxygen-free copper rod by dip coating.
Background
The oxygen-free copper rod is an important raw material for manufacturing high-end electric equipment wires such as oxygen-free electric wires and electromagnetic wire parts, and is widely used for manufacturing equipment and parts such as generating sets, transformers, traction motors, contact wires and the like. The main quality indexes for measuring the wire and the electromagnetic wire comprise tensile strength, elongation, electric conductivity, pressure resistance, oxygen content and surface quality, wherein the oxygen content is one of the main quality indexes. For the oxygen-free copper rod as the raw material for producing the lead wire and the electromagnetic wire, if the oxygen content is too high, the following phenomena can occur: oxygen in the oxygen-free copper rod exists in a copper oxide state, the copper oxide exists near a grain boundary from the aspect of a crystalline phase structure, and the copper oxide appears in the grain boundary in an inclusion form to generate negative influence on the toughness of the material, so that the mechanical property of the oxygen-free copper rod is reduced, and the oxygen-free copper rod is easy to break in subsequent processing; secondly, the existence of copper oxide can cause the reduction of the conductivity of the copper rod; annealing the processed copper product in hydrogen gas can generate bubbles and pinholes, and the surface quality is influenced; fourthly, the high pressure resistance of the product is reduced after the surface of the product has flaws.
Therefore, how to improve and reduce the oxygen content in oxygen-free copper rods has been a long-standing research hotspot. In the traditional preparation method, for example, the oxygen content in the copper wire blank or the copper rod prepared by the continuous casting and rolling method can reach 200-400 ppm, the oxygen content in the copper wire blank or the copper rod prepared by the up-drawing method can also reach 10-50 ppm, the oxygen content is high, the actual product quality is unstable, and the oxygen content of the product is suddenly high or low.
On the other hand, the present applicant has made an improvement in the Dip coating method as described in CN102615271B in the past based on the Dip Forming method described in japanese patent publication No. 49-39740 (patent document 1), japanese patent application laid-open No. 57-68263 (patent document 2), japanese patent publication No. 2-11460 (patent document 3) and japanese patent application laid-open No. 60-261658 (patent document 4), and has obtained a Dip coating method that can achieve a product quality stability to a great extent and an oxygen content of 10ppm or less with the improvement of the method.
However, with the advancement and refinement of the industry, the demand for oxygen-free copper rods has further increased. In the period from 2020 to 2021, statistics is carried out, and the oxygen content required by part of purchasers can be further controlled within less than or equal to 5ppm, so that higher-precision and high-end product or accessory manufacturing is realized.
In the actual industrialized production process of the original dip-coating method, because the batch preparation process is difficult to realize the fine control of each part, the requirements can not be stably met, after the actual implementation is based on the technical scheme recorded in CN102615271B, the actual oxygen content of the product is between 3ppm and 6ppm, the average oxygen content of the product is mostly between 4.5 ppm and 5.5 ppm, the annual average value is about 5.1ppm, and the actual result shows that the average oxygen content of the product is less than or equal to 5ppm, and even less than half of the effective product amount. Therefore, it is urgent to further improve the method to further improve the product quality.
Disclosure of Invention
The invention provides a method for preparing an oxygen-free copper rod by Dip coating, aiming at solving the problems that the prior Dip Forming method has poor product stability and uneven quality, and the prior Dip coating method can not effectively prepare the oxygen-free copper rod with ultra-low oxygen content requirement.
The invention aims to:
firstly, the dip coating method is further improved, so that the oxygen content of the oxygen-free copper rod can be further stably reduced;
secondly, the improved method is guaranteed to have simple and efficient preparation characteristics, and the oxygen-free copper rod can be guaranteed to be excellent in mechanical property;
and thirdly, the method is suitable for industrial production, and the stability of the quality of products obtained by industrial production is guaranteed.
In order to achieve the purpose, the invention adopts the following technical scheme.
A method for preparing an oxygen-free copper rod by dip coating,
the method comprises the following steps:
carrying out dip-coating treatment on the pretreated oxygen-free copper female rod by passing through molten copper dip-coating liquid, controlling the temperature and the dip-coating time of the copper dip-coating liquid in a closed container to ensure that the surface of the oxygen-free copper female rod absorbs heat and softens, then carrying out traction on the oxygen-free copper female rod after adsorbing the copper dip-coating liquid to form a copper cast rod, and carrying out post-treatment on the copper cast rod to obtain the oxygen-free copper rod;
the pretreatment comprises descaling;
the post-treatment comprises cooling, hot rolling and re-cooling in sequence;
the copper dip coating liquid, the copper casting rod and the post-treatment are protected by a reducing protective atmosphere;
the temperature of the copper dip-coating liquid is 1220-1250 ℃, and the dip-coating time is 0.5-1.3 s.
In the technical scheme of the invention, the original dip coating method is improved mainly in that the actual dip coating temperature is further changed. Because in the original dip coating scheme, the core of the method is that a thin rod with relatively high oxygen content is taken as the core, and an outer copper crystal layer with extremely low oxygen content is directly crystallized and grown on the surface of the thin rod so as to realize the reduction of the oxygen content of the whole copper rod. This approach requires the use of oxygen-free copper parent rods, which themselves have a relatively low oxygen content, and actually reduces the oxygen content in a "dilute" manner. But for the technical scheme of the invention, the invention adopts a 'replacement' mode to reduce the oxygen content by creative improvement. The melting point of copper is about 1083 ℃, theoretically, the original dip-coating scheme and the dip-coating scheme of the invention can melt the copper, but because the processing time is short and the processing speed is high, in fact, the original dip-coating scheme is to adsorb copper liquid on the surface of a mother rod after the copper on the surface is softened, so that the soft copper with high oxygen content and the almost oxygen-free copper liquid are mixed to form new copper with low oxygen content, and dilution is realized. However, according to the technical scheme of the invention, the temperature and the dip-coating time are adjusted, so that the copper on the surface of the female rod is softened, even a part of the copper is melted and enters the copper dip-coating solution, the part of the inner core which is not melted adsorbs the almost oxygen-free copper solution to replace the original high-oxygen-content copper to form new copper, and meanwhile, the copper dip-coating solution is in a high-temperature state and is continuously reduced in a reducing atmosphere, so that the copper dip-coating solution is kept in an almost oxygen-free state, the continuity of the whole production process is ensured, and the stable quality of the product can be ensured.
This is one reason why the original dip coating method cannot control the product quality very effectively, and the method of the present invention can further stabilize the product quality.
In the scheme of the invention, the fusing of the female rod is easy to generate by adopting overhigh temperature or overlong processing time, and the expected product cannot be obtained by adopting overlow temperature or overlong processing time.
As a matter of preference,
the oxygen content of the oxygen-free copper mother rod is less than or equal to 50 ppm.
Compared with the original dip-coating method which is only suitable for the master batch with the oxygen content less than or equal to 20ppm, the method can be suitable for the master batch with lower quality, and the production and manufacturing cost is reduced.
As a preference, the first and second liquid crystal compositions are,
preheating the oxygen-free copper master rod to 100-200 ℃ before the oxygen-free copper master rod passes through the molten copper dip-coating liquid;
the processes of preheating and pretreatment of the oxygen-free copper female rod and before the oxygen-free copper female rod is conveyed into the copper dip-coating liquid for dip-coating are all carried out in a reducing protective atmosphere.
Preheating can effectively and conveniently remove partial impurities on the surface of the copper plate, and the product quality can be more effectively ensured by placing the copper plate in the reducing protective atmosphere in the whole process.
As a preference, the first and second liquid crystal compositions are,
the copper dip-coating liquid is prepared by the following method:
melting an electrolytic copper plate, paving charcoal and/or graphite blocks on the copper liquid surface to form a coating, dynamically controlling the thickness of the coating to be 30-50 mm, and then introducing a reducing protective atmosphere.
In the scheme, the charcoal plays a main reducing role, and the significance of the graphite on the protection effect is more obvious. Therefore, the dual functions of charcoal and graphite can simultaneously achieve the two purposes of reducing the oxygen content and avoiding the increase of the oxygen content. In addition, the two effects can be further ensured and improved by applying a reducing protective atmosphere for assistance.
As a preference, the first and second liquid crystal compositions are,
the particle size of the charcoal and/or the graphite is 5-10 mm.
The undersize particle sizes of the charcoal and the graphite easily form impurity doping, so that the product quality is reduced, the influence on the roundness and the dimensional tolerance of the product is large, the overlarge particle sizes of the product can cause the generation of large and more stacking gaps, the contact area is small, and the actual use effect is poor.
As a preference, the first and second liquid crystal compositions are,
the electrolytic copper plate is heated and melted in a melting furnace to form copper liquid, flows into a holding furnace through a launder, is pressurized to a dip-coating crucible to be used as copper dip-coating liquid for dip-coating treatment, and is carried out in a reducing protective atmosphere in the whole process.
Likewise, the whole process is carried out in a reducing protective atmosphere to ensure that the oxygen content of the product is low.
As a preference, the first and second liquid crystal compositions are,
cleaning slag once every 20-28 days from the copper liquid in the melting furnace;
and cleaning the slag once every 25-35 days by using the copper liquid in the heat-preserving furnace.
Slag tends to increase the impurity content of the product and should be cleaned regularly.
As a matter of preference,
when the melting furnace cleans slag: the graphite tool is used to remove the coating and/or surface floating matter from the copper level and to re-add the charcoal and/or graphite.
The use of graphite tools avoids the introduction of other impurities, which is particularly easy to introduce with respect to metal tools.
As a matter of preference,
the reducing protective atmosphere contains 5-6% of VOL hydrogen and 7-9% of VOL carbon monoxide, and is prepared from incomplete combustion products of natural gas and air.
The method adopts pure hydrogen as the raw material and has relatively high cost, and the method adopts the incomplete combustion product of natural gas and air as the reductive protective gas, so that the cost can be effectively saved.
An oxygen-free copper rod is provided,
the oxygen content of the oxygen-free copper rod is less than or equal to 5.0 ppm.
The oxygen-free copper rod can meet the requirement of the current market on higher-quality oxygen-free copper rods.
The invention has the beneficial effects that:
1) the oxygen content of the oxygen-free copper rod can be further remarkably reduced, so that the oxygen-free copper rod can stably reach the condition of less than or equal to 3ppm in an experimental environment, and the high standard of less than or equal to 4ppm can be still basically met in industrial production;
2) the whole method is simple and efficient, is suitable for industrialized and continuous production and manufacture, and has practical industrial value.
The specific implementation mode is as follows:
the present invention is described in further detail below with reference to specific examples. Those skilled in the art will be able to implement the invention based on these teachings. Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
Unless otherwise specified, the raw materials used in the examples of the present invention are all commercially available or available to those skilled in the art; unless otherwise specified, the methods used in the examples of the present invention are all those known to those skilled in the art.
Unless otherwise stated, the reducing protective atmosphere used in the embodiment of the present invention is generated by a reducing protective gas, and the reducing protective gas is a product of incomplete combustion of natural gas and air, and contains 5 to 6% VOL hydrogen, 7 to 9% VOL carbon monoxide, an oxygen content of 20ppm or less, and the balance of nitrogen and impurity gases which cannot be removed.
Example 1
Smelting of a copper plate:
placing an electrolytic copper plate in a melting furnace, heating until the electrolytic copper plate is melted into copper liquid, and paving a copper liquid surface with the mass ratio of 1: 9, forming a coating by using charcoal and graphite blocks, respectively sieving the charcoal and the graphite blocks by using a 5mm sieve and a 10mm sieve, selecting the charcoal and the graphite with the particle size of 5-10 mm, wherein the initial laying thickness is about 50mm, the thickness of the coating is dynamically controlled to be 30-50 mm during the initial laying period, the graphite blocks are completely used after a small amount of black smoke is emitted from the coating, and at the moment, copper liquid in a melting furnace flows into a heat preservation furnace through a launder, so that the temperature of the copper liquid is raised to 1220 ℃ and is preserved for later use;
in the smelting process, the graphite shovel is required to be used for shoveling off the coating on the surface of the molten copper when the electrolytic copper plate is added, and the mass ratio of the graphite shovel to the coating on the surface of the molten copper is 1 after the new electrolytic copper plate is added each time: 9, the charcoal and the graphite blocks form a coating, and the particle size, the initial laying thickness, the dynamically controlled coating thickness and the subsequent steps of the charcoal and the graphite blocks are the same as the steps in the previous step;
the molten copper in the melting furnace and the heat preservation furnace needs to be cleaned regularly;
the method specifically comprises the following steps:
the melting furnace cleans the furnace slag every 25 days, a graphite shovel is used for removing the coating on the surface of the copper liquid during cleaning, and after a new electrolytic copper plate is added each time, the mass ratio of the new electrolytic copper plate to the copper liquid surface is 1: 9, forming a coating by using charcoal and graphite blocks, respectively sieving the charcoal and the graphite blocks by using a 5mm sieve and a 10mm sieve, selecting the charcoal and the graphite with the particle size of 5-10 mm, wherein the initial laying thickness is about 50mm, the thickness of the coating is dynamically controlled to be 30-50 mm during the initial laying period, and the graphite blocks are completely used after the coating emits a small amount of black smoke;
cleaning the furnace slag once every 30 days by the holding furnace, removing floating objects on the surface of the copper liquid by a graphite shovel during cleaning, and increasing the flow value of the reducing protective gas to 60m within 2h after the cleaning3/h；
In addition to the above, the melting furnace and holding furnace are each 40m3The flow rate of/h is fed with reducing protective gas.
Continuous traction manufacturing of the oxygen-free copper rod:
pretreatment: oxygen-free copper female rod (size) manufactured by the above-mentioned method
) The oxygen-free copper mother rod used in the embodiment has the oxygen content of about 32-49 ppm, and is preheated to 180 ℃ for descaling;
wire feeding and dip coating: conveying the pretreated oxygen-free copper female rod into a dip-coating crucible for constant-speed traction, introducing copper liquid in a heat preservation furnace into the dip-coating crucible as copper dip-coating liquid, and performing dip-coating treatment on the oxygen-free copper female rod;
and (3) post-treatment: cooling to 600 deg.C and hot rolling to size
The product of (1) is hot-rolled and then cooled to room temperature;
and winding to obtain the oxygen-free copper rod.
In the three processes of the pretreatment, the wire feeding, the dip coating and the post-treatment, the thickness is 40m3The flow rate/h is fed with reducing protective gas.
In the specific dip coating process:
the temperature of the copper dip-coating liquid introduced into the dip-coating crucible from the holding furnace was 1220 ℃, and the pulling speed was controlled so that the time period during which the oxygen-free copper master rod was treated in the copper dip-coating liquid was 1.0 s.
In this embodiment: the reducing protective gas is a product of incomplete combustion of natural gas and air, wherein the product contains 5% of VOL hydrogen, 8% of VOL carbon monoxide, oxygen content less than or equal to 20ppm, and the balance of nitrogen and impurity gas which cannot be removed.
And detecting the welding performance, the oxygen content, the roundness and the like of the obtained product. The results are shown in the following table:
| welding performance | Oxygen content | Average oxygen content | Roundness degree | Dimensional tolerance |
| ++ | 2.2～3.1ppm | 2.7ppm | OK | OK |
In the table: the welding performance is '+ +' which indicates that no bubble exists at a welding point during welding, '+' which indicates that the welding point is almost bubble-free during welding, '-' which indicates that the welding point generates obvious bubbles during welding; the oxygen content is shown by an upper limit value and a lower limit value of multipoint detection of each hundred meters of products, and the average oxygen content is the average value of calculation results of the oxygen content; the roundness 'OK' is that the roundness meets the standard requirement, and the 'NG' indicates that the roundness is unqualified; the dimensional tolerance "OK" is within the standard acceptable range (< 3%) and "NG" is outside the standard acceptable range.
Example 2
Smelting of a copper plate:
placing an electrolytic copper plate in a melting furnace, heating to melt the electrolytic copper plate into copper liquid, and paving a copper layer on the surface of the copper liquid according to the mass ratio of 1: 9, forming a coating by using charcoal and graphite blocks, respectively sieving the charcoal and the graphite blocks by using a 5mm sieve and a 10mm sieve, selecting the charcoal and the graphite with the particle size of 5-10 mm, wherein the initial laying thickness is about 50mm, the thickness of the coating is dynamically controlled to be 30-50 mm during the period, the graphite blocks are completely used after a small amount of black smoke is emitted from the coating, and at the moment, copper liquid in a melting furnace flows into a heat preservation furnace through a launder, so that the temperature of the copper liquid is raised to 1250 ℃ and is preserved for later use;
in the smelting process, the graphite shovel is required to be used for shoveling off the coating on the surface of the molten copper when the electrolytic copper plate is added, and the mass ratio of the graphite shovel to the coating on the surface of the molten copper is 1.5 after the new electrolytic copper plate is added each time: 8.5, forming a coating by using charcoal and graphite blocks, respectively sieving the charcoal and the graphite blocks by using a 5mm sieve and a 10mm sieve, selecting the charcoal and the graphite with the particle size of 5-10 mm, wherein the initial laying thickness is about 50mm, dynamically controlling the thickness of the coating to be 30-50 mm in the period, completely using the graphite blocks after the coating emits a small amount of black smoke, and carrying out the same subsequent steps;
the molten copper in the melting furnace and the heat preservation furnace needs to be cleaned regularly;
the method specifically comprises the following steps:
the melting furnace cleans the furnace slag once every 20 days, a graphite shovel is used for removing a coating on the surface of the copper liquid during cleaning, and after a new electrolytic copper plate is added each time, the mass ratio of the furnace slag to the copper liquid surface is 1: 9, forming a coating by using charcoal and graphite blocks, respectively sieving the charcoal and the graphite blocks by using a 5mm sieve and a 10mm sieve, selecting the charcoal and the graphite with the particle size of 5-10 mm, wherein the initial laying thickness is about 50mm, the thickness of the coating is dynamically controlled to be 30-50 mm during the initial laying period, and the graphite blocks are completely used after the coating emits a small amount of black smoke;
cleaning the furnace slag once every 25 days by the holding furnace, shoveling floating objects on the surface of the copper liquid by a graphite shovel during cleaning, and increasing the flow value of the reducing protective gas to 60m within 2h after cleaning3/h；
In addition to the above, the melting furnace and holding furnace were each charged with a reducing atmosphere at a flow rate of 40m 3/h.
Continuous traction manufacturing of the oxygen-free copper rod:
pretreatment: oxygen-free copper female rod (size) manufactured by the above-mentioned method
) The oxygen-free copper mother rod used in the embodiment has the oxygen content of 26-41 ppm, and is preheated to 100 ℃ for descaling;
wire feeding and dip coating: conveying the pretreated oxygen-free copper female rod into a dip-coating crucible for constant-speed traction, introducing copper liquid in a heat preservation furnace into the dip-coating crucible as copper dip-coating liquid, and performing dip-coating treatment on the oxygen-free copper female rod;
and (3) post-treatment: cooling to 600 deg.C and hot rolling to size
The product of (1) is hot-rolled and then cooled to room temperature;
and winding to obtain the oxygen-free copper rod.
In the three processes of the pretreatment, the wire feeding, the dip coating and the post-treatment, the thickness is 40m3The flow rate/h is fed with reducing protective gas.
In the specific dip coating process:
the temperature of the copper dip-coating liquid introduced into the dip-coating crucible from the holding furnace was 1250 ℃, and the pulling speed was controlled so that the time period for the oxygen-free copper master rod to be treated in the copper dip-coating liquid was 0.3 s.
In this embodiment: the reducing protective gas is a product of incomplete combustion of natural gas and air, wherein the product contains 5% of VOL hydrogen, 8% of VOL carbon monoxide, oxygen content less than or equal to 20ppm, and the balance of nitrogen and impurity gas which cannot be removed.
And detecting the welding performance, the oxygen content, the roundness and the like of the obtained product. The results are shown in the following table:
| welding performance | Oxygen content | Average oxygen content | Roundness degree | Dimensional tolerance |
| ++ | 2.9～3.4ppm | 3.2ppm | OK | OK |
In the table: the welding performance is '+ +' which indicates that no bubble exists at a welding point during welding, '+' which indicates that the welding point is almost bubble-free during welding, '-' which indicates that the welding point generates obvious bubbles during welding; the oxygen content is shown by an upper limit value and a lower limit value of multipoint detection of each hundred meters of products, and the average oxygen content is the average value of calculation results of the oxygen content; the roundness 'OK' is that the roundness meets the standard requirement, and the 'NG' indicates that the roundness is unqualified; the dimensional tolerance "OK" is within the standard acceptable range (< 3%) and "NG" is outside the standard acceptable range.
Example 3
Smelting of a copper plate:
placing an electrolytic copper plate in a melting furnace, heating until the electrolytic copper plate is melted into copper liquid, and paving a copper liquid surface with the mass ratio of 1: 9, forming a coating by using charcoal and graphite blocks, respectively sieving the charcoal and the graphite blocks by using a 5mm sieve and a 10mm sieve, selecting the charcoal and the graphite with the particle size of 5-10 mm, wherein the initial laying thickness is about 50mm, the thickness of the coating is dynamically controlled to be 30-50 mm during the period, the graphite blocks are completely used after a small amount of black smoke is emitted from the coating, and at the moment, copper liquid in a melting furnace flows into a heat preservation furnace through a launder, so that the temperature of the copper liquid is raised to 1250 ℃ and is preserved for later use;
in the smelting process, when the electrolytic copper plate is added, the coating on the surface of the copper liquid needs to be removed by a graphite shovel, and after a new electrolytic copper plate is added, the copper liquid surface is paved with the following components in a mass ratio of 1: 9, forming a coating by using the charcoal and the graphite blocks, respectively sieving the charcoal and the graphite blocks by using a 5mm sieve and a 10mm sieve, selecting the charcoal and the graphite with the particle size of 5-10 mm, wherein the initial laying thickness is about 50mm, dynamically controlling the thickness of the coating to be 30-50 mm in the period, completely using the graphite blocks after the coating emits a small amount of black smoke, and performing the same subsequent steps;
the molten copper in the melting furnace and the heat preservation furnace needs to be cleaned regularly;
the method specifically comprises the following steps:
the melting furnace cleans the furnace slag every 25 days, a graphite shovel is used for removing the coating on the surface of the copper liquid during cleaning, and after a new electrolytic copper plate is added each time, the mass ratio of the new electrolytic copper plate to the copper liquid surface is 1: 9, forming a coating by using charcoal and graphite blocks, respectively sieving the charcoal and the graphite blocks by using a 5mm sieve and a 10mm sieve, selecting the charcoal and the graphite with the particle size of 5-10 mm, wherein the initial laying thickness is about 50mm, the coating thickness is dynamically controlled to be 30-50 mm in the period, and the graphite blocks are used after the coating turns red and a small amount of black smoke is emitted;
the holding furnace is arranged at intervals of 30Cleaning primary slag, removing floating objects on the surface of the copper liquid by a graphite shovel during cleaning, and increasing the flow value of reducing protective gas to 60m within 2h after cleaning3/h；
In addition to the above, the melting furnace and holding furnace were each charged with a reducing atmosphere at a flow rate of 40m 3/h.
Continuous traction manufacturing of the oxygen-free copper rod:
pretreatment: oxygen-free copper female rod (size) manufactured by the above-mentioned method
) The oxygen-free copper mother rod used in the embodiment has the oxygen content of 37-48 ppm, and is preheated to 200 ℃ for descaling;
wire feeding and dip coating: conveying the pretreated oxygen-free copper female rod into a dip-coating crucible for constant-speed traction, introducing copper liquid in a heat preservation furnace into the dip-coating crucible as copper dip-coating liquid, and performing dip-coating treatment on the oxygen-free copper female rod;
and (3) post-treatment: cooling to 600 deg.C and hot rolling to size
The product of (1) is hot-rolled and then cooled to room temperature;
and winding to obtain the oxygen-free copper rod.
In the three processes of the pretreatment, the wire feeding, the dip coating and the post-treatment, the thickness is 40m3The flow rate/h is fed with reducing protective gas.
In the specific dip coating process:
the temperature of the copper dip-coating liquid introduced into the dip-coating crucible from the holding furnace was 1250 ℃, and the pulling speed was controlled so that the time for processing the oxygen-free copper master rod in the copper dip-coating liquid was 1.3 s.
In this embodiment: the reducing protective gas is a product of incomplete combustion of natural gas and air, wherein the product contains 5% of VOL hydrogen, 8% of VOL carbon monoxide, oxygen content less than or equal to 20ppm, and the balance of nitrogen and impurity gas which cannot be removed.
And detecting the welding performance, oxygen content, roundness and the like of the obtained product. The results are shown in the following table:
| welding performance | Oxygen content | Average oxygen content | Roundness degree | Dimensional tolerance |
| ++ | 3.2～4.3ppm | 3.6ppm | OK | OK |
In the table: the welding performance is '+ +' which indicates that no bubble exists at a welding point during welding, '+' which indicates that the welding point is almost bubble-free during welding, '-' which indicates that the welding point generates obvious bubbles during welding; the oxygen content is shown by an upper limit value and a lower limit value of multipoint detection of each hundred meters of products, and the average oxygen content is the average value of calculation results of the oxygen content; the roundness 'OK' is that the roundness meets the standard requirement, and the 'NG' indicates that the roundness is unqualified; the dimensional tolerance "OK" is within the standard acceptable range (< 3%) and "NG" is outside the standard acceptable range.
Scale production record 1
In the large-scale production process, a pipeline is adopted for supplying gas, the used reductive protective gas is a product of incomplete combustion of natural gas and air, and contains 5-6% of VOL hydrogen, 7-9% of VOL carbon monoxide, the oxygen content is less than or equal to 20ppm, and the balance of nitrogen and impurity gas which cannot be removed.
The production in the large furnace is carried out according to the scheme parameters of the embodiment 1, and the production record and the detection record from 6 months to 11 months in 2021 are taken as data analysis, and are specifically recorded as follows.
In the table: the welding performance is '+ +' which indicates that no bubble exists at a welding point during welding, '+' which indicates that the welding point is almost bubble-free during welding, '-' which indicates that the welding point generates obvious bubbles during welding; the average oxygen content is the average value of the calculation results of the oxygen content; the roundness NG rate is the proportion of the NG times of roundness detection to all the detection times; the tolerance NG rate is the ratio of the number of size tolerance detection NG times to the total number of detection times.
As can be seen from the data in the table, the product quality tends to be stable in the industrial production process, and because the furnace is started to be a normal and uninterrupted production process, the invention can very effectively ensure that the product roundness and the dimensional tolerance all meet the requirements along with the extension of the production time, and the average oxygen content is basically stabilized at 3.5ppm, and the welding performance is excellent.
And in 2019, 1-12 months, compared with the industrialized production of the embodiment 6 recorded in CN102615271B, the actual average oxygen content is reduced from 5.1ppm to 3.5ppm, and the high requirement that the oxygen content is less than or equal to 5ppm is achieved or even greatly exceeded. Although the yield is reduced by about 8%, the product quality is effectively improved, the overall benefit is greatly increased, and the obtained product can be used for manufacturing equipment and parts with higher requirements and completely meets the third-party purchasing standard.
Record of mass production 2
At 12 months 2021, the charcoal used was treated.
The specific treatment process sequentially comprises the following steps: removing impurities, washing with alkali and baking;
the impurity removal is carried out by adopting a flotation method to remove impurities, and charcoal and sodium hydroxide (and/or potassium hydroxide are adjusted according to the cost and have approximate effects) particles are mixed according to the mass ratio of 1: 0.3 (actual ratio 1: x, sodium hydroxide and potassium hydroxide are a and b, respectively, the calculation formula of x is
) The method comprises the following steps of mixing the raw materials according to a proportion, adding water for immersion, boiling for 45min, then baking to constant weight at 380 ℃ in a protective atmosphere, controlling the actual boiling time within 30-60 min, performing positive correlation adjustment according to a linear function of x, and adopting the above 380 ℃ in comprehensive consideration of the plant benefit.
Specifically, the production activity record data from 12 months 2021 to 1 month 2022 are as follows.
As can be seen from the above table, the quality of the product can be further improved by adjusting the charcoal. Because impurities in the charcoal easily influence the quality of the product and the quality of the charcoal easily influences the reduction capability of the charcoal during actual use, after the method is adopted, the impurities are removed and activated by the charcoal pretreatment, so that the oxygen content of the copper liquid can be effectively reduced, and the quality of the product is improved.
Comparative example 1
Based on the technical solution of embodiment 1, the adjustment is performed only in the following sections:
the pulling speed was controlled so that the oxygen-free copper parent bar was treated in the copper dip coating solution for a period of 1.5 seconds.
The phenomenon of fusing of the oxygen-free copper female rod frequently occurs in the experimental process, fusing occurs when the average traction length is 16.3m, and continuous production cannot be effectively realized.
And detecting the welding performance, oxygen content, roundness and the like of the obtained product. The results are shown in the following table:
| welding performance | Oxygen content | Average oxygen content | Roundness degree | Dimensional tolerance |
| ++ | 1.8～2.6ppm | 2.4ppm | NG | NG |
In the table: the welding performance is '+' which indicates that no bubble exists at the welding spot during welding, '+' which indicates that the welding spot almost has no bubble during welding, '-' which indicates that obvious bubble is generated at the welding spot during welding; the oxygen content is shown by an upper limit value and a lower limit value of multipoint detection of each hundred meters of products, and the average oxygen content is the average value of calculation results of the oxygen content; the roundness OK is that the roundness meets the standard requirement, and the NG indicates that the roundness is unqualified; the dimensional tolerance "OK" is within the standard acceptable range (< 3%) and "NG" is outside the standard acceptable range.
As can be seen from the table above, both the actual and average oxygen content are lower, but the actual roundness and dimensional tolerances show significant defects. The main reason is that the melting degree of the oxygen-free copper female rod is too large, so that the flatness of an actual inner core inside the oxygen-free copper female rod is poor, the adsorption effect of copper liquid at each angle is different, and the production of high-quality products cannot be realized.
Comparative example 2
Based on the technical solution of embodiment 1, the adjustment is performed only in the following sections:
the temperature of the copper dip-coating solution introduced from the holding furnace into the dip-coating crucible was 1280 ℃.
The phenomenon of fusing of the oxygen-free copper female rod frequently occurs in the experimental process, fusing occurs when the average traction length is 16.3m, and continuous production cannot be effectively realized.
And detecting the welding performance, oxygen content, roundness and the like of the obtained product. The results are shown in the following table:
| welding performance | Oxygen content | Average oxygen content | Roundness degree | Dimensional tolerance |
| ++ | 1.5～2.7ppm | 2.5ppm | NG | NG |
In the table: the welding performance is '+ +' which indicates that no bubble exists at a welding point during welding, '+' which indicates that the welding point is almost bubble-free during welding, '-' which indicates that the welding point generates obvious bubbles during welding; the oxygen content is shown by an upper limit value and a lower limit value of multipoint detection of each hundred meters of products, and the average oxygen content is the average value of calculation results of the oxygen content; the roundness 'OK' is that the roundness meets the standard requirement, and the 'NG' indicates that the roundness is unqualified; the dimensional tolerance "OK" is within the standard acceptable range (< 3%), "NG" is outside the standard acceptable range.
As can be seen from the above table, both the oxygen content and the average oxygen content are lower, but substantial roundness and dimensional tolerances show significant defects, and the average oxygen content is higher but the minimum value of the oxygen content is lower than in comparative example 1. The reason is that the temperature of the copper dip coating liquid is too high, the melting degree of the oxygen-free copper female rod is too large, and the flowing characteristics of the copper dip coating liquid are changed, so that the flatness of an actual inner core and the actual adsorption flatness inside the copper dip coating liquid are different, and the stable production of high-quality products cannot be realized.
Through long-time process improvement and orthogonal test comparison, the fact proves that the temperature of 1220-1250 ℃ is the optimal copper dip coating liquid temperature of the technical scheme of the invention, the technical effect of further reducing the oxygen content cannot be effectively realized when the temperature is lower than the optimal copper dip coating liquid temperature, and the product quality is reduced when the temperature is too high. Similarly, the short processing time cannot produce the effect, and the too long processing time easily causes the problem of product quality reduction such as wire breakage. The actual temperature of the copper immersion plating liquid is strictly regulated according to 1220-1250 ℃, the problems of wire breakage and the like can be basically avoided in the interval, and the treatment duration is actually regulated according to the wire diameter of the oxygen-free copper female rod.
In conclusion, the invention breaks through the technical limit that the prior dip coating technology is only used for diluting oxygen, realizes the replacement effect, more effectively reduces the oxygen content in the oxygen-free copper rod, leads the oxygen content to reach the standard of more than or equal to 5.0ppm, and has great industrial significance.
Claims (10)
1. A method for preparing an oxygen-free copper rod by dip coating, which is characterized in that,
the method comprises the following steps:
carrying out dip-coating treatment on the pretreated oxygen-free copper female rod by passing through molten copper dip-coating liquid, controlling the temperature and the dip-coating time of the copper dip-coating liquid in a closed container to ensure that the surface of the oxygen-free copper female rod absorbs heat and softens, then carrying out traction on the oxygen-free copper female rod after adsorbing the copper dip-coating liquid to form a copper cast rod, and carrying out post-treatment on the copper cast rod to obtain the oxygen-free copper rod;
the pretreatment comprises descaling;
the post-treatment comprises cooling, hot rolling and re-cooling in sequence;
the copper dip-coating liquid, the copper casting rod and the post-treatment are protected by a reducing protective atmosphere;
the temperature of the copper dip-coating liquid is 1220-1250 ℃, and the dip-coating time is 0.5-1.3 s.
2. The method for preparing oxygen-free copper rod by dip coating according to claim 1,
the oxygen content of the oxygen-free copper master rod is less than or equal to 50 ppm.
3. The method for producing oxygen-free copper rods by dip coating according to claim 1 or 2,
preheating the oxygen-free copper master rod to 100-200 ℃ before the oxygen-free copper master rod passes through the molten copper dip-coating liquid;
the processes of preheating and pretreatment of the oxygen-free copper female rod and before the oxygen-free copper female rod is conveyed into the copper dip-coating liquid for dip-coating are all carried out in a reducing protective atmosphere.
4. The method for preparing oxygen-free copper rod by dip coating according to claim 1,
the copper dip-coating solution is prepared by the following method:
melting an electrolytic copper plate, paving charcoal and/or graphite blocks on the copper liquid surface to form a coating, dynamically controlling the thickness of the coating to be 30-50 mm, and then introducing a reducing protective atmosphere.
5. The method for preparing oxygen-free copper rod by dip coating according to claim 4,
the particle size of the charcoal and/or the graphite is 5-10 mm.
6. The method for producing oxygen-free copper rods by dip coating according to claim 4 or 5,
the electrolytic copper plate is heated and melted in a melting furnace to form copper liquid, flows into a holding furnace through a launder, is pressurized to a dip-coating crucible to be used as copper dip-coating liquid for dip-coating treatment, and is carried out in a reducing protective atmosphere in the whole process.
7. The method for preparing oxygen-free copper rod by dip coating according to claim 6,
cleaning slag once every 20-28 days from the copper liquid in the melting furnace;
and cleaning the slag once every 25-35 days by using the copper liquid in the heat-preserving furnace.
8. The method for preparing oxygen-free copper rod by dip coating according to claim 7,
when the melting furnace cleans slag: the graphite tool is used to remove the coating and/or surface floating matter from the copper level and to re-add the charcoal and/or graphite.
9. The method for producing oxygen-free copper rods by dip coating according to claim 1 or 4,
the reducing protective atmosphere contains 5-6% of VOL hydrogen and 7-9% of VOL carbon monoxide, and is prepared from incomplete combustion products of natural gas and air.
10. An oxygen-free copper rod made by the method of any of claims 1 to 9, wherein the oxygen content of the oxygen-free copper rod is 5ppm or less.
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