WO2015180500A1 - Procédé pour la production de produit plaqué à chaud par laminage à chaud, laminage à froid direct sans décapage et recuit de réduction - Google Patents

Procédé pour la production de produit plaqué à chaud par laminage à chaud, laminage à froid direct sans décapage et recuit de réduction Download PDF

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WO2015180500A1
WO2015180500A1 PCT/CN2015/070983 CN2015070983W WO2015180500A1 WO 2015180500 A1 WO2015180500 A1 WO 2015180500A1 CN 2015070983 W CN2015070983 W CN 2015070983W WO 2015180500 A1 WO2015180500 A1 WO 2015180500A1
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hot
rolling
reduction
dip
rolled
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PCT/CN2015/070983
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English (en)
Chinese (zh)
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李俊
谭宁
孟庆格
关闯
史良权
何晓明
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宝山钢铁股份有限公司
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Priority to DE112015002553.7T priority Critical patent/DE112015002553T5/de
Priority to JP2016570338A priority patent/JP6498219B2/ja
Priority to RU2016152001A priority patent/RU2690866C2/ru
Priority to KR1020167034949A priority patent/KR102337241B1/ko
Publication of WO2015180500A1 publication Critical patent/WO2015180500A1/fr

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    • 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
    • C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
    • C23C2/0222—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating in a reactive atmosphere, e.g. oxidising or reducing atmosphere
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226—Hot rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236—Cold rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0273—Final recrystallisation annealing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • C21D9/54—Furnaces for treating strips or wire
    • C21D9/56—Continuous furnaces for strip or wire
    • 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
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
    • 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
    • C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
    • C23C2/0224—Two or more thermal pretreatments
    • 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
    • C23C2/024—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by cleaning or etching
    • 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
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C2/12—Aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C2/40—Plates; Strips
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F17/00—Multi-step processes for surface treatment of metallic material involving at least one process provided for in class C23 and at least one process covered by subclass C21D or C22F or class C25
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/19—Iron or steel

Definitions

  • the invention relates to a method for producing a hot-dip product, in particular to a method for producing a hot-rolled, acid-free direct cold rolling reduction annealing hot-dip product.
  • the production of cold-rolled hot-dip galvanized products is that the hot-rolled sheet is first passed through the acid rolling unit to remove the scale of the hot-rolled sheet, and the cold-rolled sheet is deformed to a suitable thickness.
  • the hot-dip plating first removes the grease, then reduces the annealing and then completes the heat.
  • this traditional hot-dip galvanizing product has a long production process, low production efficiency, and serious environmental pollution problems caused by the pickling process, which is the biggest obstacle for steel companies in energy conservation and environmental protection.
  • the removal of a large amount of iron oxide during the pickling process results in low product yield, strong corrosive acid requirements for production equipment, and waste acid treatment, resulting in increased production and maintenance costs. Therefore, the development of acid-free hot-dip galvanizing products and production processes, that is, the omission of the pickling process, has always been the dream of thin-belt manufacturers, and is of great significance to the sustainable development of steel companies.
  • Patent No. US6258186B1 and KR100905653B1 disclose a method for high-speed production of acid-free hot-dip hot-dip galvanizing products.
  • the basic principle is to use a reducing gas such as hydrogen to reduce the surface of the hot-rolled strip by replacing the pickling, but the reduction rate of the scale is higher.
  • the patent controls the cooling rate in the hot rolling strip coiling process to increase the ferrous oxide content in the oxide by more than 20%. Because ferrous oxide is easier to reduce, but the effect is very limited, the reduction rate and efficiency still restrict the development of the entire technology.
  • Japanese Patent No. 06-033449 discloses a "Tight Scale" steel sheet.
  • the surface of the steel sheet is mainly composed of triiron tetroxide, and the structure is dense, and the subsequent deep processing deformation process
  • the iron oxide scale deforms together with the steel sheet without falling off, and satisfies the user's use of the iron oxide scale, and does not involve the subsequent cold rolling with the iron oxide scale.
  • 201010235928.X, 201010298939.2, 200710010183.5, 201010010116.5, 201010209526.2, 201010189410.7 and 200510047958.7 disclose a method for producing steel for pickling-free automobile beam, which is controlled by a hot rolling process to make the surface of the hot rolled sheet mainly by four. Composition of triiron oxide.
  • the above patents all relate to the direct use of hot-rolled strip iron oxide scale, and the hot-rolled sheet with iron oxide scale is bent, does not involve cold rolling deformation, and does not involve subsequent hot-dip galvanizing or hot-dip plating of other alloys.
  • the object of the present invention is to provide a method for producing a hot-rolled, acid-free direct cold-rolling reduction-annealed hot-dip product by hot rolling and cold rolling, which can be omitted for hot rolling and cold rolling. Washing and related processes to achieve environmentally-friendly hot-dip products with short processes, high efficiency and low cost.
  • the iron oxide structure on the surface of the hot-rolled sheet is mainly composed of Fe 3 O 4 and FeO, and the thickness of the scale is thin, and it is subjected to cold rolling with iron oxide scale, and is subjected to hot-plating and the like.
  • the method for producing a hot-rolled, pickling-free direct-rolling reduction-annealed hot-dip product of the present invention comprises the following steps:
  • Hot rolling by hot rolling mill After dephosphorizing the slab, it is successively subjected to coarse rolling by roughing mill, finish rolling of finishing mill, cooling of cooling device, coiling of coiler and reduction of scale by reducing the temperature of the tapping furnace and increasing the rolling speed. Thickness, simultaneous control of post-rolling cooling rate and coiling temperature to control the surface structure of the hot-rolled sheet, improve the adhesion of the scale and reduce the thickness of the scale;
  • Cold rolling by cold rolling mill By optimizing the cold rolling process parameters including rolling pressure, tension, deformation rate and rolling pass, and using rolling lubricating fluid, the iron oxide scale undergoes good plastic deformation with the matrix during cold rolling. , thereby obtaining a high surface quality and a plate shape with an iron oxide sheet;
  • Reductive annealing through a reduction furnace introducing a reducing gas and controlling the reduction temperature and time, completely reducing the scale, and cooling to the strip to enter the zinc pot temperature;
  • Hot dip plating After reduction annealing, directly enter the zinc pot and stay for a few seconds to complete the hot plating.
  • an alkaline degreasing agent is used in the degreasing and rinsing machine to remove oil and dust remaining on the surface during cold rolling, and rinsed and dried.
  • the tapping temperature is 1100-1250 ° C
  • the finishing temperature is 800-900 ° C
  • the coiling temperature is between 550-600 ° C
  • the rolling speed is 8-20 m / s
  • the cooling rate after rolling is 7 -30 ° C / s.
  • the tapping temperature is 1150-1200 ° C
  • the finishing temperature is 840-870 ° C
  • the coiling temperature is 550-570 ° C
  • the rolling speed is 14-18 m / s
  • the cooling rate is 15-20 ° C / s.
  • the tapping temperature is 1170 or 1200 ° C
  • the finishing temperature is 850 or 860 ° C
  • the coiling temperature is 550 or 560 ° C
  • the rolling speed is 17 or 18 m/s
  • the cooling rate is 19 or 20 ° C / s.
  • the obtained hot rolled sheet has a thickness of 1.0-6 mm; the surface of the hot rolled sheet has an average thickness of 5-10 ⁇ m, and the scale of the scale is mainly Fe 3 O 4 and FeO, wherein the Fe 3 O 4 weight The content accounts for more than 50%.
  • the hot rolled sheet has a thickness of 1.5 to 4 mm, and the Fe 3 O 4 content accounts for 65% or more.
  • the rolling is completed in 1-2 passes, and the deformation rate per pass is controlled to be 1.0% to 90%.
  • the rolling is completed in one pass, and the deformation rate is controlled to be 50% - 80%.
  • the rolling emulsion is deionized water or palm oil, and the cold rolling reduction ratio is 1.0% to 90%.
  • the cold rolling reduction ratio is 50%-80%.
  • the reduction temperature is 500-1000 ° C
  • the reduction time is 60-300 s
  • the reducing gas is H 2 or a mixture of CO and an inert gas, wherein the concentration of H 2 or CO is not less than 3%.
  • the reduction temperature is 750-950 ° C
  • the residence time is 120-300 s
  • the H 2 or CO concentration is 10%-75%.
  • the reduction temperature is 800 ° C, 850 ° C or 900 ° C
  • the residence time is 180 s, 240 s or 300 s
  • the H 2 or CO concentration is 15%, 25% or 30%.
  • the resulting hot-dip products include hot-dip pure zinc, hot-dip galvanized aluminum-magnesium, hot-dip aluminum-zinc or hot-dip aluminum-silicon products.
  • the method for producing the hot-rolled acid-free direct-rolling reduction-annealing hot-dip plating product of the present invention omits the pickling unit compared with the conventional process, and is a short-flow, high-efficiency process, and the performance meets the actual demand;
  • the traditional galvanizing technology does not require acid washing to remove the scale, and does not involve any corrosive medium such as hydrochloric acid or sulfuric acid, which fundamentally solves the environmental pollution problem caused by pickling; the present invention can obtain hot-plated products of different thickness specifications.
  • FIG. 1 is a schematic view showing a process route of a method for producing a hot-rolled, pickling-free direct-rolling reduction-annealed hot-dip product according to an embodiment of the present invention
  • Example 3 is a photograph showing the surface topography of the scale of the hot-rolled sheet obtained by applying Example 1 of the present invention after 50% cold rolling;
  • Figure 4 is a cross-sectional scan photograph of the galvanized sheet obtained in Application Example 1 of the present invention.
  • Figure 5 is a photograph of the surface of the galvanized sheet obtained by applying the first embodiment of the present invention after 180° bending;
  • Figure 6 is a cross-sectional scan of the galvanized aluminum-magnesium sheet obtained in Application Example 2 of the present invention.
  • FIG. 1 is a schematic view showing a process route of a method for producing a hot-rolled, pickling-free direct-rolling reduction-annealed hot-dip product according to an embodiment of the present invention. As shown in the drawing, the method for producing a galvanized product includes the following steps.
  • Hot rolling by hot rolling mill After removing the phosphorus by the hot rolled sheet 1, the rough rolling mill 2 rough rolling, the finishing rolling mill 3 finishing rolling, the cooling device 4 cooling, the coiler 5 winding, and the lowering of the tapping temperature are successively performed. Increase the rolling speed to reduce the thickness of the scale, control the cooling rate and coiling temperature after rolling, control the structure of the scale on the surface of the hot rolled sheet, and improve the adhesion of the scale to obtain a thinner and specific iron oxide structure.
  • the hot-rolled sheet can not only improve the reduction speed, but also ensure complete reduction, and is also beneficial for the hot-rolled strip with iron oxide scale for cold rolling without peeling off.
  • an alkaline degreasing agent is used to remove oil and dust remaining on the surface during the cold rolling process, and is rinsed and dried.
  • pure water is used as the rolling liquid in the cold rolling process, it is not necessary to use an alkaline degreasing agent in this process.
  • the furnace temperature is controlled to 1100-1250 ° C
  • the final rolling temperature is controlled to 800-900 ° C
  • the coiling temperature is controlled between 550-600 ° C
  • the rolling speed is controlled.
  • the cooling rate after rolling is controlled to 7-30 ° C / s.
  • the tapping temperature is 1150 to 1200 ° C
  • the finishing temperature is 840-870 ° C
  • the coiling temperature is 550-570 ° C
  • the rolling speed is 14-18 m/s
  • the cooling rate is 15-20 ° C/s.
  • the tapping temperature is 1170 or 1200 ° C
  • the finishing temperature is 850 or 860 ° C
  • the coiling temperature is 550 or 560 ° C
  • the rolling speed is 17 or 18 m/s
  • the cooling rate is 19 or 20 ° C/s.
  • the thickness of the hot rolled sheet obtained by the above control is 1.0-6 mm, preferably 1.5-4 mm, and the thickness is much smaller than that of the prior art, and the average thickness of the scale of the hot rolled sheet surface is 5-10 ⁇ m (the average scale of the scale of the hot rolled sheet)
  • Thickness refers to the representative position of the hot rolled sheet such as the head, the middle, the tail and the side, etc., each position takes at least three points, and the total thickness of the scale measured at each point is divided by the total number of measuring points. The result is the average thickness).
  • the iron oxide structure is mainly composed of Fe 3 O 4 and FeO, wherein the Fe 3 O 4 content is 50% by weight or more, preferably 65% or more. In this way, the thickness of the scale is thinner, which is favorable for reduction, good adhesion, and favorable for strip cold rolling.
  • the rolling emulsion is deionized water or palm oil emulsion, and the cold rolling reduction ratio is 1.0% to 100%, preferably, the cold rolling reduction ratio is 50% to 80%.
  • the rolling is completed in 1-2 passes, and the deformation rate per pass is controlled at 1.0%-100%. More preferably, the rolling is completed in one pass and the deformation rate is controlled in the range of 50% to 80%.
  • the iron oxide scale can be well plastically deformed with the substrate during the cold rolling process, thereby obtaining a high surface quality and a plate-shaped iron oxide coated sheet without peeling off, sticking, and the like.
  • the reducing gas is H 2 or a mixture of CO and an inert gas, wherein the concentration of H 2 or CO is not less than 3%.
  • the reduction temperature is 750-950 ° C
  • the residence time is 120-300 s
  • the H 2 or CO concentration is 10%-75%.
  • the original temperature is 800 ° C, 850 ° C or 900 ° C
  • the residence time is 180 s, 240 s or 300 s
  • the H 2 or CO concentration is 15%, 25% or 30%.
  • the iron oxide scale is reduced to pure iron, which improves the metal yield, and the reducing gas H 2 or CO is oxidized to H 2 O or CO 2 without causing secondary pollution to the environment, and is not involved.
  • the reacted H 2 or CO can be recycled.
  • the hot-dip products obtained in the above step (5) include hot-dip pure zinc, hot-dip galvanized aluminum-magnesium, hot-dip aluminum-zinc, hot-dip aluminized silicon, and other hot-dip alloy products.
  • the slab is heated to 1200 ° C, the furnace stays for 180 min, the temperature of the furnace is 1100 ° C, the high-pressure water removes phosphorus, the phosphorus removal is followed by rough rolling, the second high-pressure water dephosphorization, and then the finishing rolling, the finishing rolling temperature is 980 ° C
  • the final rolling temperature is 870 ° C
  • the coiling temperature is 600 ° C
  • the rolling speed is 20 m / s
  • the cooling speed after rolling is 8 ° C / s
  • the obtained hot rolled sheet thickness is 3.6 mm
  • the average thickness of the surface scale is about 8 ⁇ m.
  • the content of ferric oxide is at least 50%.
  • the hot-rolled sheet is directly cold-rolled with iron oxide scale, cold-rolled to 1.8 mm thick, and the deformation rate is 50%. It is cleaned with alkali solution (if pure water is used for rolling lubrication) No need to wash with alkali, only hot water wash), and blow dry, then enter the reduction furnace, reduction temperature 1000 ° C, time 60s, hydrogen concentration 20%, cooled to 460 ° C or so into the zinc pot, stay 3s, complete hot-dip galvanizing, A hot-dip galvanized product of about 1.8 mm is obtained.
  • alkali solution if pure water is used for rolling lubrication
  • the metallographic micrograph of the iron oxide skin section of the hot-rolled sheet obtained in Example 1 after 50% cold rolling is shown in Fig. 2.
  • the thickness of the scale is thinned and starts to become discontinuous, but there is no significant phenomenon that the scale is peeled off or pressed into the substrate.
  • the surface morphology of the scale of the scale is shown in Fig. 3.
  • the oxides i.e., scales
  • the cross-sectional scan of the galvanized sheet obtained in Example 1 is shown in the figure.
  • the iron oxide scale is basically reduced completely, and there is no obvious residual iron oxide scale; the surface of the obtained galvanized sheet after 180° bending is shown in Fig. 5, the adhesion of the coating layer is good, and there is no obvious crack or zinc layer falling off phenomenon.
  • the slab is heated to 1230 ° C, the residence time in the furnace is 210 min, the tapping temperature is 1170 ° C, the high-pressure water removes phosphorus, the phosphorus removal is followed by rough rolling, the secondary high-pressure water dephosphorization, and then the finishing rolling, the finishing rolling and rolling temperature 930 °C, the final rolling temperature is 850 ° C, the coiling temperature is 560 ° C, the rolling speed is 12 m / s, the cooling rate after rolling is 20 ° C / s, the thickness of the obtained hot rolled sheet is 3.05 mm, and the average thickness of the surface scale is about 7 ⁇ m.
  • the content of triiron tetroxide is at least 65%.
  • the hot-rolled sheet is directly subjected to cold rolling with iron oxide skin, cold-rolled to 2.9 mm, and the deformation rate is 5%, which is washed with alkali liquid (if it is not necessary to carry out rolling lubrication with pure water) Alkaline washing, only hot water cleaning), and blow dry, then enter the reduction furnace, reduction temperature 800 ° C, time 180s, hydrogen concentration 50%, cooled to 470 ° C or so into the zinc pot, stay 5s, complete hot-dip galvanized aluminum magnesium , obtained a hot-dip galvanized aluminum-magnesium product of about 2.90 mm thickness.
  • Fig. 6 is a cross-sectional view showing the obtained galvanized aluminum-magnesium plate. The plating layer is continuous and complete, and the scale is completely reduced.
  • the energy spectrum analysis is as shown in Table 1.
  • the slab is heated to 1180 ° C, the furnace stays for 250 min, the tapping temperature is 1200 ° C, the high-pressure water removes phosphorus, the phosphorus removal is followed by rough rolling, the second high-pressure water dephosphorization, and then the finishing rolling, the finishing rolling and rolling temperature is 950 ° C , the final rolling temperature is 800 ° C, the coiling temperature is 550 ° C, the rolling speed is 10 m / s, the cooling rate after rolling is 30 °C / s, the obtained hot-rolled sheet has a thickness of 4 mm, and the surface oxide scale has an average thickness of about 5 ⁇ m, wherein the content of triiron tetroxide is at least 70%.
  • the hot-rolled plate is directly subjected to cold rolling with iron oxide scale, the deformation rate is 70%, it is washed with alkali solution (without alkali washing with water), blown dry, and then enters the reduction furnace, and the reduction temperature 600 ° C, time 300s, hydrogen concentration 20%, cooled to about 465 ° C into the zinc pot, stay 3s, complete hot-dip galvanizing, plating composition 1.2Al wt%-Zn, to obtain about 2.9mm hot-dip aluminum zinc products.
  • the slab is heated to 1200 ° C, the furnace stays for 200 min, the tapping temperature is 1250 ° C, the high-pressure water removes phosphorus, the phosphorus removal is followed by rough rolling, the second high-pressure water dephosphorization, and then the finishing rolling, the finishing rolling temperature is 980 ° C
  • the final rolling temperature is 880 ° C
  • the coiling temperature is 570 ° C
  • the rolling speed is 18 m / s
  • the cooling rate after rolling is 12 ° C / s
  • the thickness of the obtained hot rolled sheet is 3.6 mm
  • the average thickness of the surface scale is about 8 ⁇ m.
  • the content of ferric oxide is at least 50%.
  • the hot-rolled sheet is directly cold-rolled with iron oxide scale, cold-rolled to 1.5 mm thick, and the deformation rate is 58%. It is cleaned with lye (if pure water is used for rolling lubrication) No need for alkaline washing, only hot water cleaning), and blow dry, then enter the reduction furnace, reducing temperature 900 ° C, time 120s, hydrogen concentration 20%, cooling to 460 ° C or so into the zinc pot, stay 3s, complete hot-dip galvanizing, The zinc liquid component is 1.6Al wt%-1.6Mg-Zn%, and a hot-dip galvanized aluminum-magnesium product of about 1.2 mm is obtained.
  • the furnace temperature is 1230°C, the furnace stays for 200min, the tapping temperature is 1190°C, the high-pressure water removes phosphorus, the phosphorus removal is followed by rough rolling, the second high-pressure water dephosphorization, and then the finishing rolling, the finishing rolling and rolling temperature is 950°C, and the final rolling
  • the temperature is 900 ° C
  • the coiling temperature is 550 ° C
  • the rolling speed is 21 m / s
  • the cooling rate after rolling is 15 ° C / s
  • the thickness of the obtained hot rolled sheet is 3.6 mm
  • the average thickness of the surface scale is about 8 ⁇ m, of which the oxidized three
  • the iron content is at least 50%.
  • the hot-rolled sheet is directly cold-rolled with iron oxide scale, cold-rolled to 1.5 mm thick, and the deformation rate is 58%. It is cleaned with lye (if pure water is used for rolling lubrication) No need to wash with alkali, only hot water wash), and blow dry, then enter the reduction furnace, reducing temperature 900 ° C, time 120s, hydrogen concentration 20%, cooling to 680 ° C or so into the zinc pot, stay 3s, zinc composition 11Siwt% -Al%, obtaining a hot-dip aluminum silicon product of about 1.2 mm.
  • the present invention controls the surface of the hot-rolled sheet by controlling the hot-rolling process to perform the cold-rolling of the hot-rolled strip with iron oxide scale, so that the scale is plastically deformed without peeling during the cold rolling deformation process. Then, a reducing gas (CO or H 2 ) is reacted with the iron oxide scale to form metallic iron, and finally hot-dip galvanizing.
  • a reducing gas CO or H 2
  • the process omits the pickling and related processes. Since the iron oxide scale is not washed away by acid, no corrosive medium such as hydrochloric acid or sulfuric acid is involved, which fundamentally solves the environmental pollution caused by pickling.
  • the problem is a short-flow, high-efficiency, low-cost environmentally-friendly hot-dip galvanizing process with performance that meets actual needs.
  • the hot rolling acid-free direct-rolling reduction annealing annealing hot-dip product production method of the invention can obtain hot-dip products with different thickness specifications, especially thick-scale hot-dip galvanizing products; the obtained products are particularly suitable for surface quality requirements are not high Corrosion and mechanical properties have certain requirements, such as various construction steel, steel for electric power facilities, highways and various bridge guardrails, storage and steel for workshops.

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Abstract

L'invention concerne un procédé pour la production d'un produit plaqué à chaud par laminage à chaud, laminage à froid direct sans décapage et recuit de réduction. Le procédé comprend : un laminage à chaud, dans lequel une tôle d'acier subit un laminage de dégrossissage, un laminage de finition, un refroidissement et un enroulage, l'épaisseur d'une peau d'oxyde de fer est réduite grâce à la réduction de la température de coulée et à l'augmentation de la vitesse de laminage et la vitesse de refroidissement après enroulage et la température d'enroulage sont réglées ; un laminage à froid, dans lequel une bonne déformation plastique de la peau d'oxyde de fer conjointement avec le substrat se produit pendant le processus de laminage à froid et des phénomènes tels que l'écaillage et le collage au cylindre ne se produisent pas grâce à l'optimisation de paramètres du processus de laminage à froid tels que la pression de laminage, la tension, le taux de déformation et le nombre de passes de laminage et l'utilisation d'un fluide de lubrification de laminage approprié ; un recuit de réduction, dans lequel une réduction est effectuée pendant 60 à 300 s à 500 à 1000 oC, un gaz réducteur est amené à passer pour parfaitement réduire la peau d'oxyde de fer et un refroidissement à une température permettant à un feuillard d'acier d'entrer dans un bain de zinc est effectué ; un placage par immersion à chaud, dans lequel après le recuit de réduction, le feuillard d'acier entre directement dans le bain de zinc pendant plusieurs secondes et une galvanisation par immersion à chaud est effectuée. La présente invention permet d'éviter un décapage et des processus apparentés, ce qui permet de mettre en œuvre une production de produit plaqué à chaud à processus court, à haute efficacité, à faible coût et respectueuse de l'environnement.
PCT/CN2015/070983 2014-05-30 2015-01-19 Procédé pour la production de produit plaqué à chaud par laminage à chaud, laminage à froid direct sans décapage et recuit de réduction WO2015180500A1 (fr)

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JP2016570338A JP6498219B2 (ja) 2014-05-30 2015-01-19 熱間圧延、酸洗不要の直接冷間圧延、還元アニール、および溶融めっきにより得られた製品の製造方法
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CN115449712A (zh) * 2022-09-14 2022-12-09 浙江东南新材科技有限公司 一种高强度的酸洗板及其制备方法
CN115449712B (zh) * 2022-09-14 2023-06-09 浙江东南新材科技有限公司 一种高强度的酸洗板及其制备方法
CN116103597A (zh) * 2023-03-15 2023-05-12 燕山大学 一种热镀铝锌过程锌锅内温度变化预报方法

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JP6498219B2 (ja) 2019-04-10
CN105297033A (zh) 2016-02-03
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JP2017523301A (ja) 2017-08-17
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