WO2015180500A1 - 热轧免酸洗直接冷轧还原退火热镀产品的生产方法 - Google Patents

热轧免酸洗直接冷轧还原退火热镀产品的生产方法 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)
French (fr)
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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 KR1020167034949A priority Critical patent/KR102337241B1/ko
Priority to JP2016570338A priority patent/JP6498219B2/ja
Priority to DE112015002553.7T priority patent/DE112015002553T5/de
Priority to RU2016152001A priority patent/RU2690866C2/ru
Publication of WO2015180500A1 publication Critical patent/WO2015180500A1/zh

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    • 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
    • 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
    • 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

本发明是一种热轧免酸洗直接冷轧还原退火热镀产品的生产方法，包括：热轧，钢板经过粗轧、精轧、冷却、卷取并通过降低出炉温度、提高轧制速度来降低氧化铁皮厚度，同时控制轧后冷却速度和卷取温度；冷轧，通过优化轧制压力、张力、变形率和轧制道次等冷轧工艺参数，并采用合适的轧制润滑液，使氧化铁皮在冷轧过程中随基体发生良好塑性变形而不出现剥落、粘辊等现象；还原退火，在500-1000℃下还原60-300s，通入还原性气体对氧化铁皮还原彻底，冷却至带钢进入锌锅温度；以及热浸镀，还原退火后，直接进入锌锅，并停留数秒，完成热镀锌。本发明可省略酸洗及相关工序，实现短流程、高效率、低成本的环保型热镀产品生产。

Description

热轧免酸洗直接冷轧还原退火热镀产品的生产方法 技术领域
本发明涉及一种热镀产品生产方法，具体涉及一种热轧免酸洗直接冷轧还原退火热镀产品的生产方法。
背景技术
长期以来冷轧热镀锌产品的生产是热轧板首先经过酸轧机组，去除热轧板表面氧化铁皮，冷轧变形至合适厚度，热浸镀时先碱洗脱脂，再还原退火然后完成热镀锌，这种传统的热镀锌产品生产工艺流程长，生产效率低，而且酸洗工序带来的环境污染问题严重，是钢铁企业在节能环保方面的最大障碍。另外酸洗过程中去除大量铁氧化物造成产品成材率低，强腐蚀酸对生产设备的要求，以及废酸处理等环节，造成生产及维护成本增高。因此，开发免酸洗热镀锌产品和生产工艺，即省略酸洗工序，一直是薄带生产企业的梦想，对钢铁企业的可持续发展具有重要意义。
专利号为US6258186B1和KR100905653B1公开了高速生产免酸洗热轧热镀锌产品的方法，基本原理是采用还原气体如氢气对热轧带钢表面氧化铁皮还原代替酸洗，但由于氧化铁皮还原速度较慢，影响整个生产线运行，为了加快还原速率，实现还原与镀锌的速度匹配，该专利通过控制热轧带钢卷取过程中的冷却速度，以提高氧化物中氧化亚铁含量在20％以上，因为氧化亚铁较容易被还原，但效果非常有限，还原速率及效率仍制约着整个技术的发展。
针对热轧板表面氧化铁皮的使用性能研究，日本专利号为06-033449公开了一种“Tight Scale”钢板，该钢板表面氧化铁皮主要由四氧化三铁组成，结构致密，在后续深加工变形过程中氧化铁皮与钢板一起变形而不脱落，满足用户带氧化铁皮使用，不涉及后续带氧化铁皮的冷轧。中国专利申请号为201010235928.X，201010298939.2，200710010183.5，201010010116.5，201010209526.2，201010189410.7与200510047958.7公开了生产免酸洗汽车大梁用钢的方法，均通过控制热轧工艺过程使热轧板表面氧化铁皮主要由四氧化三铁组成。以上专利所涉及的都是热轧板带氧化铁皮的直接使用，并且带氧化铁皮的热轧板变形场合是折弯，不涉及冷轧变形，也不涉及后续热镀锌或热镀其它合金。
发明内容
本发明的目的是针对传统热镀锌工艺的不足，提供一种热轧免酸洗直接冷轧还原退火热镀产品的生产方法，通过热轧、冷轧后直接还原再热镀，可省略酸洗及相关工序，实现短流程、高效率、低成本的环保型热镀产品生产。另外，热轧板表面的氧化铁皮结构主要以Fe3O4和FeO为主，并氧化铁皮厚度较薄，通过带氧化铁皮的冷轧，且进行热镀等相关工艺。
本发明的热轧免酸洗直接冷轧还原退火热镀产品的生产方法，包括如下步骤：
通过热轧机组进行热轧：将板坯除磷后，依次经过粗轧机粗轧、精轧机精轧、冷却装置冷却、卷取机卷取并通过降低出炉温度、提高轧制速度来降低氧化铁皮厚度，同时控制轧后冷却速度和卷取温度，以控制热轧板表面氧化铁皮结构，提高氧化铁皮粘附力并降低氧化铁皮厚度；
通过冷轧机组进行冷轧：通过优化冷轧工艺参数包括轧制压力、张力、变形率和轧制道次，并采用轧制润滑液，使氧化铁皮在冷轧过程中随基体发生良好塑性变形，从而得到高表面质量和板形的带氧化铁皮板；
通过还原炉进行还原退火：通入还原性气体并控制还原温度及时间，将氧化铁皮还原彻底，并冷却至带钢进入锌锅温度；
热浸镀：还原退火后，直接进入锌锅，并停留数秒，完成热镀。
还包括在冷轧步骤后的脱脂步骤：在脱脂漂洗机中采用碱性脱脂剂去除冷轧过程中表面残留的油污及粉尘，并漂洗，烘干。
在热轧步骤中，出炉温度为1100-1250℃，终轧温度为800-900℃，卷取温度为550-600℃之间，轧制速度为8-20m/s，轧后冷却速度为7-30℃/s。
所述的出炉温度为1150-1200℃，终轧温度为840-870℃，卷取温度为550-570℃，轧制速度为14-18m/s，冷却速度为15-20℃/s。
所述的出炉温度为1170或1200℃，终轧温度为850或860℃，卷取温度为550或560℃，轧制速度为17或18m/s，冷却速度为19或20℃/s。
在热轧步骤中，获得的热轧板厚度为1.0-6mm；热轧板表面氧化铁皮的平均厚度为5-10μm，氧化铁皮结构以Fe3O4和FeO为主，其中Fe3O4重量含量占50％以上。
所述热轧板厚度为1.5-4mm，所述Fe3O4含量占65％以上。
在冷轧步骤中，轧制在1-2道次内完成，每道次变形率控制在1.0％-90％。
所述的轧制在1道次内完成，变形率控制在50％-80％。
在冷轧步骤中，轧制乳化液采用去离子水或棕榈油，冷轧压下率为1.0％-90％。
所述的冷轧压下率为50％-80％。
在还原退火步骤中，还原温度为500-1000℃，还原时间为60-300s；还原性气体为H2或CO与惰性气体的混合物，其中H2或CO的浓度不低于3％。
所述的还原温度为750-950℃，停留时间为120-300s；H2或CO浓度为10％-75％。
所述的还原温度为800℃、850℃或900℃，停留时间为180s、240s或300s；H2或CO浓度为15％、25％或30％。
在还原退火步骤中，未参与反应的H2或CO将循环使用。
在热浸镀的步骤中，所得热镀产品包括热镀纯锌、热镀锌铝镁、热镀铝锌或热镀铝硅产品。
本发明的热轧免酸洗直接冷轧还原退火热镀产品的生产方法，相比传统工艺，省略了酸洗机组，是一种短流程、高效率的工艺，且性能满足实际需求；相比传统的镀锌技术，不用酸洗除氧化铁皮，不涉及任何腐蚀性介质如盐酸、硫酸，从根本上解决了酸洗带来的环境污染问题；本发明可得到不同厚度规格的热镀产品，特别是厚规格热镀锌产品；且所得产品特别适合于对表面质量要求不高，耐蚀性和机械性能有一定要求的场合，如各种建筑用钢、电力设施用钢、高速公路和各种桥梁护栏、仓储及厂房用钢等领域。
附图说明
图1是本发明一个实施例的热轧免酸洗直接冷轧还原退火热镀产品的生产方法的工艺路线示意图；
图2是本发明应用实施例1中所得热轧板经50％冷轧后氧化铁皮断面金相显微照片；
图3是本发明应用实施例1中所得热轧板经50％冷轧后氧化铁皮表面形貌照片；
图4是本发明应用实施例1中所得镀锌板的断面扫描照片；
图5是本发明应用实施例1中所得镀锌板180°折弯后镀层表面照片；
图6是本发明应用实施例2中所得镀锌铝镁板的断面扫描。
具体实施方式
为让本发明的上述目的、特征和优点能更明显易懂，以下结合附图对本发 明的具体实施方式作详细说明。首先需要说明的是，本发明并不限于下述具体实施方式，本领域的技术人员应该从下述实施方式所体现的精神来理解本发明，各技术术语可以基于本发明的精神实质来作最宽泛的理解。在附图中相同的附图标记表示相同的部分。
图1是本发明一个实施例的热轧免酸洗直接冷轧还原退火热镀产品的生产方法的工艺路线示意图，如图所示，该镀锌产品生产方法包括如下步骤。
(1)通过热轧机组进行热轧：热轧板1除磷后，依次经过粗轧机2粗轧、精轧机3精轧、冷却装置4冷却、卷取机5卷取，并通过降低出炉温度，提高轧制速度来降低氧化铁皮厚度，同时控制轧后冷却速度和卷取温度，控制热轧板表面氧化铁皮结构，提高氧化铁皮粘附力，以得到较薄的且具有特定氧化铁皮结构的热轧板，如此可不但有利于提高还原速度，保证还原彻底，而且还有利于热轧板带氧化铁皮进行冷轧时不剥落。
(2)通过冷轧机组进行冷轧：热轧板进行带氧化铁皮冷轧，根据需要轧至适当厚度，轧制过程调节轧制参数，通过优化轧制压力、张力、变形率和轧制道次等冷轧工艺参数，并采用合适的轧制润滑液，保证氧化铁皮在冷轧过程中随基体发生良好塑性变形而不出现剥落、粘辊等现象，得到高表面质量和板形的带氧化铁皮板。
(3)通过脱脂漂洗机6进行脱脂：采用碱性脱脂剂去除冷轧过程中表面残留的油污及粉尘，并漂洗、烘干。当冷轧过程采用纯水为轧制液时，本工序无需采用碱性脱脂剂。
(4)通过还原退火炉进行还原退火：进入还原炉后经加热段7、均热段8，通入还原性气体，并在500-1000℃下还原60-300s的温度和时间双重控制下，将氧化铁皮还原彻底，再经冷却段9冷却至带钢进入锌锅温度，一般在460℃左右。
(5)进入热镀锌槽10进行热浸镀：还原退火后，直接进入热镀锌槽10(即锌锅)，并停留数秒，完成热镀。
经过多次反复试验和计算，在上述步骤(1)中出炉温度控制为1100-1250℃，终轧温度控制为800-900℃，卷取温度控制为550-600℃之间，轧制速度控制为8-20m/s，轧后冷却速度控制为7-30℃/s。优选地，出炉温度为1150-1200℃，终轧温度为840-870℃，卷取温度为550-570℃，轧制速度为14-18m/s，冷却速度为15-20℃/s。更佳的，出炉温度为1170或1200℃，终轧温度为850或860℃，卷取温度为550或560℃，轧制速度为17或18m/s，冷却速度为19或20℃/s。通过上述控制所获得的热轧板厚度为1.0-6mm，优选地，1.5-4mm， 厚度远小于现有技术，热轧板表面氧化铁皮的平均厚度为5-10μm(热轧板表面氧化铁皮平均厚度指在热轧板代表性位置如头部、中部、尾部和边部等，每个位置取至少三个点，并将各点所测氧化铁皮厚度的总和除以测量点的总个数，所得结果即为其平均厚度)。该氧化铁皮结构以Fe3O4和FeO为主，其中Fe3O4重量含量占50％以上，优选地，占65％以上。如此，使得该氧化铁皮厚度较薄，有利于还原，粘附力好，有利于带皮冷轧。
在上述步骤(2)中，轧制乳化液采用去离子水或棕榈油乳化液，冷轧压下率为1.0％-100％，优选地，冷轧压下率为50％-80％。轧制在1-2道次内完成，每道次变形率控制在1.0％-100％。更佳地，轧制在1道次内完成，变形率控制在50％-80％。
通过上述冷轧控制，可使氧化铁皮在冷轧过程中随基体发生良好塑性变形，从而得到高表面质量和板形的带氧化铁皮板，且不出现剥落、粘辊等现象。
在上述步骤(4)中，还原性气体为H2或CO与惰性气体的混合物，其中H2或CO的浓度不低于3％。优选地，还原温度为750-950℃，停留时间为120-300s；H2或CO浓度为10％-75％。更佳的，原温度为800℃、850℃或900℃，停留时间为180s、240s或300s；H2或CO浓度为15％、25％或30％。
在上述步骤(4)中氧化铁皮被还原成纯铁，提高了金属收得率，同时还原气体H2或CO被氧化成H2O或CO2，不会对环境造成二次污染，未参与反应的H2或CO可以循环使用。
在上述步骤(5)中所得热镀产品包括热镀纯锌、热镀锌铝镁、热镀铝锌、热镀铝硅及其它热镀合金产品。
下面将结合应用实施例并结合附图对本发明所述的热轧板免酸洗直接冷轧还原热镀锌工艺技术做进一步的详细说明。
实施例1
将板坯加热至1200℃，炉内停留180min，出炉温度为1100℃，高压水除磷，除磷后进行粗轧，二次高压水除磷，再进行精轧，精轧开轧温度980℃，终轧温度为870℃，卷取温度为600℃，轧制速度为20m/s，轧后冷却速度8℃/s，所得热轧板厚度为3.6mm，表面氧化铁皮平均厚度约8μm，其中四氧化三铁含量至少50％。用乳化液或纯水做润滑剂，将热轧板直接进行带氧化铁皮冷轧，冷轧轧至1.8mm厚，变形率为50％，采用碱液清洗(若用纯水进行轧制润滑时无需碱洗，只需热水清洗)，并吹干，然后进入还原炉，还原温度1000℃，时间60s，氢气浓度20％，冷却至460℃左右进入锌锅，停留3s，完成热镀锌， 获得1.8mm左右的热镀锌产品。
实施例1中所得热轧板经50％冷轧后氧化铁皮断面金相显微照片如图2所示，氧化铁皮厚度减薄，开始变得不连续，但无明显氧化铁皮脱落或压入基板现象。其氧化铁皮表面形貌照片如图3所示，氧化物(即氧化铁皮)沿轧制方向呈条状分布，开始变得不连续分布；实施例1中所得镀锌板的断面扫描照片如图4所示，氧化铁皮基本还原彻底，无明显残留氧化铁皮；所得镀锌板180°折弯后镀层表面照片如图5所示，镀层附着力良好，无明显裂纹或锌层脱落现象。
实施例2
将板坯加热至1230℃，炉内停留时间210min，出炉温度为1170℃，高压水除磷，除磷后进行粗轧，二次高压水除磷，再进行精轧，精轧开轧温度930℃，终轧温度为850℃，卷取温度为560℃，轧制速度为12m/s，轧后冷却速度20℃/s，所得热轧板厚度为3.05mm，表面氧化铁皮平均厚度约7μm，其中四氧化三铁含量至少65％。用乳化液或纯水作为轧制液，将热轧板直接进行带氧化铁皮冷轧，冷轧至2.9mm，变形率为5％，采用碱液清洗(若用纯水进行轧制润滑时无需碱洗，只需热水清洗)，并吹干，然后进入还原炉，还原温度800℃，时间180s，氢气浓度50％，冷却至470℃左右进入锌锅，停留5s，完成热镀锌铝镁，获得2.90mm厚度左右的热镀锌铝镁产品。图6示出其所得镀锌铝镁板的断面扫描图，镀层连续完整，氧化铁皮还原彻底，其能谱分析如表1所列。
表1 能谱分析
Figure PCTCN2015070983-appb-000001
实施例3
将板坯加热至1180℃，炉内停留250min，出炉温度为1200℃，高压水除磷，除磷后进行粗轧，二次高压水除磷，再进行精轧，精轧开轧温度950℃，终轧温度为800℃，卷取温度为550℃，轧制速度为10m/s，轧后冷却速度30 ℃/s，所得热轧板厚度为4mm，表面氧化铁皮平均厚度约5μm，其中四氧化三铁含量至少70％。用乳化液或纯水做润滑剂，将热轧板直接进行带氧化铁皮冷轧，变形率为70％，采用碱液清洗(用水无需碱洗)，并吹干，然后进入还原炉，还原温度600℃，时间300s，氢气浓度20％，冷却至465℃左右进入锌锅，停留3s，完成热镀锌，镀液成分1.2Al wt％-Zn,获得2.9mm左右的热镀铝锌产品。
实施例4
将板坯加热至1200℃，炉内停留200min，出炉温度为1250℃，高压水除磷，除磷后进行粗轧，二次高压水除磷，再进行精轧，精轧开轧温度980℃，终轧温度为880℃，卷取温度为570℃，轧制速度为18m/s，轧后冷却速度12℃/s，所得热轧板厚度为3.6mm，表面氧化铁皮平均厚度约8μm，其中四氧化三铁含量至少50％。用乳化液或纯水做润滑剂，将热轧板直接进行带氧化铁皮冷轧，冷轧轧至1.5mm厚，变形率为58％，采用碱液清洗(若用纯水进行轧制润滑时无需碱洗，只需热水清洗)，并吹干，然后进入还原炉，还原温度900℃，时间120s，氢气浓度20％，冷却至460℃左右进入锌锅，停留3s，完成热镀锌，锌液成分1.6Al wt％-1.6Mg-Zn％,获得1.2mm左右的热镀锌铝镁产品。
实施例5
出炉温度1230℃，炉内停留200min，出炉温度为1190℃,高压水除磷，除磷后进行粗轧，二次高压水除磷，再进行精轧，精轧开轧温度950℃，终轧温度为900℃，卷取温度为550℃，轧制速度为21m/s，轧后冷却速度15℃/s，所得热轧板厚度为3.6mm，表面氧化铁皮平均厚度约8μm，其中四氧化三铁含量至少50％。用乳化液或纯水做润滑剂，将热轧板直接进行带氧化铁皮冷轧，冷轧轧至1.5mm厚，变形率为58％，采用碱液清洗(若用纯水进行轧制润滑时无需碱洗，只需热水清洗)，并吹干，然后进入还原炉，还原温度900℃，时间120s，氢气浓度20％，冷却至680℃左右进入锌锅，停留3s，锌液成分11Siwt％-Al％,获得1.2mm左右的热镀铝硅产品。
经实践证明，实施例2-5与实施例1一样，均可正常获得符合期望的热镀产品，且无明显漏镀或镀层脱落现象。
综上所述，本发明通过调整热轧工艺控制热轧板表面氧化铁皮结构，进行热轧板带氧化铁皮冷轧，使氧化铁皮在冷轧变形过程中随基体发生塑性变形而不发生剥落，然后借助还原性气体(CO或H2)与氧化铁皮反应生成金属铁， 最后进行热镀锌。与传统热镀锌工艺相比，该工艺省略了酸洗及相关工序，由于不用酸洗除氧化铁皮，不涉及任何腐蚀性介质如盐酸、硫酸，从根本上解决了酸洗带来的环境污染问题，是一种短流程、高效率、低成本的环保型热镀锌生产工艺，且性能满足实际需求。
本发明的热轧免酸洗直接冷轧还原退火热镀产品的生产方法，可得到不同厚度规格的热镀产品，特别是厚规格热镀锌产品；所得产品特别适合于对表面质量要求不高，耐蚀性和机械性能有一定要求的场合，如各种建筑用钢、电力设施用钢、高速公路和各种桥梁护栏、仓储及厂房用钢等领域。
要注意的是，以上列举的仅为本发明的具体实施例，显然本发明不限于以上实施例，随之有着许多的类似变化。本领域的技术人员如果从本发明公开的内容直接导出或联想到的所有变形，均应属于本发明的保护范围。也即应理解，在阅读了本发明的上述讲授内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。

Claims (16)

  1. 一种热轧免酸洗直接冷轧还原退火热镀产品的生产方法，其特征在于，包括如下步骤：
    通过热轧机组进行热轧：将板坯除磷后，依次经过粗轧机粗轧、精轧机精轧、冷却装置冷却、卷取机卷取并通过降低出炉温度、提高轧制速度来降低氧化铁皮厚度，同时控制轧后冷却速度和卷取温度，以控制热轧板表面氧化铁皮结构，提高氧化铁皮粘附力并降低氧化铁皮厚度；
    通过冷轧机组进行冷轧：通过优化冷轧工艺参数包括轧制压力、张力、变形率和轧制道次，并采用轧制润滑液，使氧化铁皮在冷轧过程中随基体发生良好塑性变形，从而得到高表面质量和板形的带氧化铁皮板；
    通过还原炉进行还原退火：通入还原性气体并控制还原温度及时间，将氧化铁皮还原彻底，并冷却至带钢进入锌锅温度；
    热浸镀：还原退火后，直接进入锌锅，并停留数秒，完成热镀。
  2. 根据权利要求1所述的热轧免酸洗直接冷轧还原退火热镀产品的生产方法，其特征在于：还包括在冷轧步骤后的脱脂步骤：在脱脂漂洗机中采用碱性脱脂剂去除冷轧过程中表面残留的油污及粉尘，并漂洗，烘干。
  3. 根据权利要求1所述的热轧免酸洗直接冷轧还原退火热镀产品的生产方法，其特征在于：在热轧步骤中，出炉温度为1100-1250℃，终轧温度为800-900℃℃，卷取温度为550-600℃之间，轧制速度为8-20m/s，轧后冷却速度为7-30℃/s。
  4. 根据权利要求3所述的热轧免酸洗直接冷轧还原退火热镀产品的生产方法，其特征在于：所述的出炉温度为1150-1200℃，终轧温度为840-870℃，卷取温度为550-570℃，轧制速度为14-18m/s，冷却速度为15-20℃/s。
  5. 根据权利要求3或4所述的热轧免酸洗直接冷轧还原退火热镀产品的生产方法，其特征在于：所述的出炉温度为1170或1200℃，终轧温度为850或860℃，卷取温度为550或560℃，轧制速度为17或18m/s，冷却速度为19或20℃/s。
  6. 根据权利要求1中任一项所述的热轧免酸洗直接冷轧还原退火热镀产品的生产方法，其特征在于：在热轧步骤中，获得的热轧板厚度为1.0-6mm；热轧 板表面氧化铁皮的平均厚度为5-10μm，氧化铁皮结构以Fe3O4和FeO为主，其中Fe3O4重量含量占50％以上。
  7. 根据权利要求6所述的热轧免酸洗直接冷轧还原退火热镀产品的生产方法，其特征在于：所述热轧板厚度为1.5-4mm，所述Fe3O4含量占65％以上。
  8. 根据权利要求1所述的热轧免酸洗直接冷轧还原退火热镀产品的生产方法，其特征在于：在冷轧步骤中，轧制在1-2道次内完成，每道次变形率控制在1.0％-90％。
  9. 根据权利要求8所述的热轧免酸洗直接冷轧还原退火热镀产品的生产方法，其特征在于：所述的轧制在1道次内完成，变形率控制在50％-80％。
  10. 根据权利要求1或8所述的热轧免酸洗直接冷轧还原退火热镀产品的生产方法，其特征在于：在冷轧步骤中，轧制乳化液采用去离子水或棕榈油，冷轧压下率为1.0％-90％。
  11. 根据权利要求10所述的热轧免酸洗直接冷轧还原退火热镀产品的生产方法，其特征在于：所述的冷轧压下率为50％-80％。
  12. 根据权利要求1所述的热轧免酸洗直接冷轧还原退火热镀产品的生产方法，其特征在于：在还原退火步骤中，还原温度为500-1000℃，还原时间为60-300s；还原性气体为H2或CO与惰性气体的混合物，其中H2或CO的浓度不低于3％。
  13. 根据权利要求12所述的热轧免酸洗直接冷轧还原退火热镀产品的生产方法，其特征在于：所述的还原温度为750-950℃，停留时间为120-300s；H2或CO浓度为10％-75％。
  14. 根据权利要求12或13所述的热轧免酸洗直接冷轧还原退火热镀产品的生产方法，其特征在于：所述的还原温度为800℃、850℃或900℃，停留时间为180s、240s或300s；H2或CO浓度为15％、25％或30％。
  15. 根据权利要求12所述的热轧免酸洗直接冷轧还原退火热镀产品的生产方法，其特征在于：在还原退火步骤中，未参与反应的H2或CO将循环使用。
  16. 根据权利要求1所述的热轧免酸洗直接冷轧还原退火热镀产品的生产方法，其特征在于：在热浸镀的步骤中，所得热镀产品包括热镀纯锌、热镀锌铝镁、热镀铝锌或热镀铝硅产品。
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CN106909723A (zh) * 2017-02-16 2017-06-30 燕山大学 冷轧过程乳化液流量与轧制速度关系曲线优化设定方法
CN106909723B (zh) * 2017-02-16 2020-03-31 燕山大学 冷轧过程乳化液流量与轧制速度关系曲线优化设定方法
CN112417639A (zh) * 2020-09-15 2021-02-26 东北大学 一种热轧低碳钢氧化铁皮结构演变数字解析方法
CN112417639B (zh) * 2020-09-15 2023-08-04 东北大学 一种热轧低碳钢氧化铁皮结构演变数字解析方法
CN113088855A (zh) * 2021-03-31 2021-07-09 山东钢铁集团日照有限公司 一种cq级薄规格镀锌板的高速稳定生产方法
CN113136537A (zh) * 2021-03-31 2021-07-20 首钢京唐钢铁联合有限责任公司 一种提高热基镀锌带钢表面质量的方法
CN114480805A (zh) * 2021-12-09 2022-05-13 鞍钢股份有限公司 一种控制热轧o5板表面质量的方法
CN115074623A (zh) * 2022-06-16 2022-09-20 唐山钢铁集团高强汽车板有限公司 一种耐氢致开裂的镀锌热冲压用钢及其生产方法
CN115074623B (zh) * 2022-06-16 2023-08-25 唐山钢铁集团高强汽车板有限公司 一种耐氢致开裂的镀锌热冲压用钢及其生产方法
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
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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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