WO2015180463A1 - 带氧化物层的热镀产品、其制造方法及其应用 - Google Patents

带氧化物层的热镀产品、其制造方法及其应用 Download PDF

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WO2015180463A1
WO2015180463A1 PCT/CN2014/094612 CN2014094612W WO2015180463A1 WO 2015180463 A1 WO2015180463 A1 WO 2015180463A1 CN 2014094612 W CN2014094612 W CN 2014094612W WO 2015180463 A1 WO2015180463 A1 WO 2015180463A1
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Prior art keywords
hot
oxide layer
dip
product
reduction
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English (en)
French (fr)
Inventor
李俊
谭宁
关闯
马新建
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Baoshan Iron and Steel Co Ltd
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Baoshan Iron and Steel Co Ltd
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Priority to JP2017514762A priority Critical patent/JP6903572B2/ja
Priority to KR1020167034951A priority patent/KR102333168B1/ko
Priority to RU2016151998A priority patent/RU2689402C2/ru
Publication of WO2015180463A1 publication Critical patent/WO2015180463A1/zh
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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
    • 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
    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • 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
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • 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
    • C23C2/50—Controlling or regulating the coating processes

Definitions

  • the invention relates to a hot-dip product and a manufacturing method thereof, in particular to a hot-dip product with an oxide layer, a manufacturing method thereof and an application thereof.
  • Hot-dip products are widely used in automotive, home appliance, construction, machinery manufacturing and other industries for their excellent corrosion resistance; as the market demands for corrosion resistance of products, the demand for hot-dip products has gradually surpassed that of cold-rolled bare boards.
  • the steel plate In the traditional hot-dip galvanizing production process, the steel plate must be pickled before hot-dip galvanizing. The purpose is to remove the surface oxide of the steel plate by means of sulfuric acid or hydrochloric acid. Otherwise, the residual iron oxide scale will directly affect the wettability of the zinc liquid, thereby affecting the hot-dip plating. Adhesion and continuity of the zinc layer on the surface of the product. Therefore, the conventional hot-dip product structure has a zinc layer directly attached to the surface of the steel substrate, and a thin Fe 2 Al 5 transition layer exists at the interface, and the transition layer mainly serves as an adhesion function to enhance the adhesion of the zinc layer to the steel sheet.
  • the main problem faced by the existing process is that the waste acid and acid mist generated by pickling will cause environmental pollution to become more and more serious.
  • the pickling and related processes also result in high production cost and low production efficiency.
  • the pickling and hot-plating processes are not productive. Matching, had to divide the production of several units and other issues.
  • the object of the present invention is to provide a hot-dip product with an oxide layer which is low in cost and excellent in corrosion resistance, a manufacturing method thereof and an application thereof for the conventional hot-dip product and the production process, and it is not necessary to remove the oxidation by a pickling process.
  • the layer of matter allows the residual oxide layer to act as a corrosion protection layer to further protect the substrate to retard corrosion.
  • a method for producing a hot-dip product having an oxide layer which in turn includes a step of smelting, casting, hot rolling, reduction annealing, and hot dip plating, wherein the reduction annealing step is obtained in a hot rolling step.
  • the hot rolled sheet with iron oxide skin layer enters the reduction annealing furnace without pickling, so that the annealing furnace.
  • the hot-rolled sheet in the hot-rolled sheet is reduced to a metallic iron by the protective atmosphere of the reducing gas and the reducing temperature, and the metal iron produced by the reduction is present in the outermost layer of the hot-rolled steel sheet base.
  • a reduced iron layer is formed; and the hot rolled sheet having the reduced iron layer is further subjected to a hot dip galvanizing step to form a hot-dip product having an oxide layer.
  • a cold rolling step is further added between the hot rolling and the reduction annealing step, and the cold rolled sheet with iron oxide obtained in the cold rolling step is directly subjected to reduction annealing without being acid washed into the reduction annealing furnace.
  • the tapping temperature is 1100-1250 ° C
  • the finishing rolling temperature is 800-900 ° C
  • the coiling temperature is 550-650 ° C
  • the rolling speed is 8-20 m/s
  • the reduction annealing step The reduction temperature is 500 to 1000 ° C
  • the residence time is 30 s to 300 s
  • the reducing gas is H 2 or a mixture of CO and an inert gas.
  • 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 tapping temperature is 1170 ° C or 1200 ° C
  • the finishing temperature is 850 ° C or 860 ° C
  • the coiling temperature is 550 ° C or 560 ° C
  • the rolling speed is 17 m / s or 18 m / s.
  • the reduction temperature is 750-950 ° C and the residence time is 120-300 s.
  • the reduction temperature is 800 ° C, 850 ° C or 900 ° C, and the residence time is 180 s, 240 s or 300 s.
  • the inert gas is any one of N 2 , Ar, He, and the concentration of H 2 or CO is not less than 3%.
  • the concentration of H2 or CO is from 20% to 75%.
  • the thickness of the reduced iron layer is controlled to be 0.5 ⁇ m to 5 ⁇ m by controlling the reduction annealing temperature, the holding time, and the reducing gas concentration to increase the thickness of the reduced iron layer produced by the reduction.
  • a hot-dip product with an oxide layer which is a steel substrate, a reduced iron layer, and a hot-dip coating layer from the inside to the outside, wherein the product further includes a capable product a protective layer for delaying corrosion of the steel substrate, the protective layer being located between the steel substrate and the reduced iron layer, wherein the protective layer is an oxide layer composed of an iron oxide scale, and the reduced iron layer is a surface layer of the iron oxide scale Part of the metal iron that has been reduced by annealing.
  • the oxide in the oxide layer contains any one, two or more of FeO, Fe 3 O 4 , and Fe 2 O 3 .
  • the oxide layer is continuous or semi-continuous and has an average thickness of from 0.1 to 5 ⁇ m.
  • the reduced iron layer has an average thickness of 0.5 to 5 ⁇ m.
  • composition of the hot dip coating is pure Zn, Zn-Al, Zn-Al-Mg, Zn-Al-Mg-Si or Al-Si alloy.
  • the hot dip coating has an average thickness of 5-20 ⁇ m.
  • the hot-dip product is applied to steel for construction, steel for highway guardrails or steel for storage.
  • the hot-dip-coated hot-oxidation product manufactured by the method of the invention has the structure of steel base, protective layer, reduced iron layer and zinc layer from the inside to the outside, wherein the protective layer is composed of its own iron oxide scale, It can further protect the steel substrate from corrosion and can delay corrosion.
  • the protective layer is composed of its own iron oxide scale
  • it can further protect the steel substrate from corrosion and can delay corrosion.
  • it has a protective barrier, so it has stronger corrosion resistance and is especially suitable for high corrosion resistance.
  • the degree of deformation is not complicated, such as construction steel, highway guardrails, storage steel, etc.
  • the present invention omits pickling and related processes, and can completely solve the problem of pollutants such as waste acid, which is energy-saving and environmentally friendly, and is the general trend.
  • the hot-dip product with oxide layer produced by the method of the invention has strong economic advantages, has strong application and promotion, does not involve production line transformation and new equipment, and is fully applicable to the traditional hot-dip galvanizing production line. .
  • Figure 1 is a scanning electron micrograph of a section of a conventional hot-dip product
  • FIG. 2 is a scanning electron micrograph of a cross section of a hot-dip product according to a first embodiment of the method for producing a hot-dip product with an oxide layer of the present invention
  • FIG. 3 is a cross-sectional scanning electron micrograph of a hot-dip product of a second embodiment manufactured by the method for producing a hot-dip product with an oxide layer of the present invention
  • Figure 4 is a cross-sectional scanning electron micrograph of a hot-dip product according to a third embodiment of the method for producing a hot-dip product with an oxide layer of the present invention
  • Fig. 5 is a scanning electron micrograph of a cross section of a hot-dip product according to a fourth embodiment of the method for producing a hot-dip product with an oxide layer of the present invention.
  • the method for manufacturing a hot-dip product with an oxide layer comprises: smelting, casting steel slab, hot-rolled or cold-rolled steel sheet, reduction annealing, hot dip coating, wherein reduction annealing is heat with iron oxide scale
  • reduction annealing is heat with iron oxide scale
  • the rolled or cold-rolled sheet enters the reduction annealing furnace without pickling, and the surface layer of the scale is reduced to metallic iron under the protective atmosphere of the reducing gas and controlled by a certain temperature, and the metal iron produced by the reduction exists in the most
  • the outer layer forms a reduced iron layer, and the remaining scale forms an oxide layer, which is hot dip galvanized or other alloy to form a hot-dip product with an oxide layer.
  • the hot rolling has a tapping temperature of 1100-1250 ° C, a finishing temperature of 800-900 ° C, a coiling temperature of 550-650 ° C, a rolling speed of 8-20 m/s, and a reduction annealing reduction temperature of 500.
  • residence time is 30 s-300 s
  • reducing gas is H 2 or a mixture of CO and inert gas.
  • 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 reduction temperature is 750 -950 ° C
  • residence time is 120-300 s.
  • the tapping temperature is 1170 ° C or 1200 ° C
  • the finishing temperature is 850 ° C or 860 ° C
  • the coiling temperature is 550 ° C or 560 ° C
  • the rolling speed is 17 m / s or 18 m / s
  • the reduction temperature is 800 ° C, 850 ° C or 900 ° C
  • the residence time is 180 s, 240 s or 300 s.
  • the inert gas is N 2 , Ar or He, wherein the concentration of H 2 or CO is not less than 3%, preferably, the concentration of H 2 or CO is from 20% to 75%.
  • the freshly produced reduced iron thickness is increased by a comprehensive equilibrium setting of the reduction annealing temperature, the holding time, and the H 2 concentration, and the average thickness thereof is ensured to be 0.5 ⁇ m to 5 ⁇ m.
  • a hot-dip product with an oxide layer prepared by the above method is a steel substrate, a protective layer, a reduced iron layer, and a hot-dip coating in this order from the inside to the outside.
  • the layer is an oxide layer composed of a reduced iron oxide scale, and the reduced iron layer is composed of a metal layer of a surface layer of the scale oxide which is subjected to reduction annealing, and the protective layer can delay corrosion of the steel substrate.
  • the oxide of the above oxide layer contains one or two or more of FeO, Fe 3 O 4 , and Fe 2 O 3 , and is mainly FeO.
  • the oxide layer is continuous or discontinuous and has an average thickness of from 0.1 to 5 ⁇ m.
  • the reduced iron layer produced by the reduction has an average thickness of 0.5 to 5 ⁇ m.
  • the hot dip coating has an average thickness of 5-20 ⁇ m.
  • the composition of the hot dip coating may be pure Zn, Zn-Al, Zn-Al-Mg, Zn-Al-Mg-Si, Al-Si or other alloys.
  • the hot-dip products prepared above can be applied to steel for construction, steel for highway guardrails or steel for storage.
  • the slab after smelting, casting and dephosphorization is hot rolled, the tapping temperature is 1100 ° C, the finishing temperature is 850 ° C, the coiling temperature is 550 ° C, the rolling speed is 20 m / s, and the final thickness of the hot rolled sheet is 2.2. Mm, the thickness of the scale is 6 ⁇ m on average.
  • the slab after smelting, casting and dephosphorization is hot rolled, the tapping temperature is 1150 ° C, the finishing temperature is 870 ° C, the coiling temperature is 580 ° C, the rolling speed is 15 m / s, and the final thickness of the hot rolled sheet is 2.0. Mm, the thickness of the scale is 7 ⁇ m on average.
  • the reduction temperature is 800 ° C
  • the time is 180 s
  • the hydrogen concentration is 20%
  • the hot-dip galvanizing is completed in the zinc pot at 460 ° C.
  • the zinc liquid composition is 0.13 wt% Al-Zn.
  • the cross-sectional microstructure of the obtained galvanized sheet is shown in Fig. 3.
  • Figure 3 shows that, likewise, there is a continuous layer of oxide between the galvanized layer and the steel substrate.
  • the slab after smelting, casting and dephosphorization is hot rolled, the tapping temperature is 1200 ° C, the finishing temperature is 900 ° C, the coiling temperature is 600 ° C, the rolling speed is 8 m / s, and the final thickness of the hot rolled sheet is 3.0. Mm, the thickness of the scale is 8 ⁇ m on average.
  • the cross-sectional microstructure of the zinc plate is shown in Fig. 4.
  • the elemental analysis results of the position shown in Fig. 4 are shown in Table 1 below. Spectrum 1 represents the residual oxide layer, Spectrum 2 represents the reduced iron layer, and Spectrum 3 represents the reaction of reduced iron with zinc. The resulting alloy layer.
  • the quantity represents the weight percentage
  • the slab after smelting, casting and dephosphorization is hot rolled, the tapping temperature is 1250 ° C, the finishing temperature is 900 ° C, the coiling temperature is 600 ° C, the rolling speed is 10 m / s, and the final thickness of the hot rolled sheet is 3.0. Mm, the thickness of the scale is 8 ⁇ m on average.
  • the hot-rolled sheet is subjected to hot rolling with scale, and the deformation amount is 5%. It enters the reduction annealing furnace, the reduction temperature is 800 ° C, the time is 60 s, the hydrogen concentration is 20%, and the hot-dip galvanizing is completed in the zinc pot at 460 ° C.
  • the zinc liquid composition is 0.2% Al- Zn, the cross-sectional microstructure of the obtained galvanized sheet is shown in FIG.
  • the slab after smelting, casting and dephosphorization is hot rolled, the tapping temperature is 1250 ° C, the finishing temperature is 900 ° C, the coiling temperature is 600 ° C, the rolling speed is 10 m / s, and the final thickness of the hot rolled sheet is 3.0. Mm, the thickness of the scale is 8 ⁇ m on average.
  • the hot-rolled sheet is cold-rolled with scale, and the deformation is 5%. It enters the reduction annealing furnace, the reduction temperature is 800 ° C, the time is 60 s, the hydrogen concentration is 20%, and the hot-dip aluminum zinc is completed in the zinc pot at 620 ° C.
  • the zinc liquid composition is 55% Al. -Zn.
  • the slab after smelting, casting and dephosphorization is hot rolled, the tapping temperature is 1250 ° C, the finishing temperature is 900 ° C, the coiling temperature is 600 ° C, the rolling speed is 10 m / s, and the final thickness of the hot rolled sheet is 3.0. Mm, the thickness of the scale is 8 ⁇ m on average.
  • the hot-rolled sheet was subjected to scale rolling with a scale of 5%, and was subjected to a reduction annealing furnace at a reduction temperature of 800 ° C for 60 s, a hydrogen concentration of 20%, and a hot-dip aluminized silicon at 680 ° C, and a plating composition of 11% Si-Al.
  • the hot-dip coated oxide product produced by the method of the present invention has a structure of steel plate, oxide, reduced iron and hot-dip coating from the inside to the outside, wherein the oxide itself acts as a protective layer and can be used for the substrate.
  • Iron plays a certain protective role and can delay corrosion.
  • it has a protective barrier, so it has stronger corrosion resistance. It is especially suitable for high corrosion resistance and the degree of deformation is not complicated.
  • the present invention also omits pickling and related processes, and can completely solve the problem of pollutants such as waste acid, which is energy-saving and environmentally friendly, and is the general trend.
  • the oxide hot-dip product produced by the method of the invention has strong economic advantages, has strong application and popularization, does not involve production line transformation and new equipment, and is fully applicable to the traditional hot-dip galvanizing production line.

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Abstract

一种带氧化物层的热镀产品、其制造方法及其应用。该制造方法依次包括：冶炼、铸造钢板坯、冷轧或热轧钢板、还原退火、热浸镀锌，其中还原退火是将钢板不经酸洗直接进入还原退火炉，在还原性气体的保护性气氛和一定温度下将氧化物表层部分还原成金属铁,使新还原产生的金属铁存在于最外层；热浸镀后形成带氧化物层的热镀产品。该热镀产品自里向外依次是钢基板、保护层、还原铁、热浸镀层，其中，保护层由本身的氧化物层构成。

Description

带氧化物层的热镀产品、其制造方法及其应用 技术领域
本发明涉及一种热镀产品及其制造方法，具体涉及的是一种带氧化物层的热镀产品、其制造方法及其应用。
背景技术
热镀产品以其优良的耐蚀性广泛应用于汽车、家电、建筑、机械制造等行业；随着市场对产品耐蚀性能要求的提高，热镀产品的需求量已逐渐超过冷轧裸板。
传统热镀锌生产过程中，钢板在热镀锌前必须经过酸洗，目的是借助硫酸或盐酸将钢板表面氧化物清除干净，否则残留氧化铁皮会直接影响锌液的浸润性，进而影响热镀产品表面锌层的附着性及连续性。因此传统热镀产品结构是锌层直接附着于钢基板表面，界面上有一薄薄的Fe2Al5过渡层存在，过渡层主要起粘附作用，增强锌层对钢板的附着力。现有工艺面临的主要问题是酸洗产生的废酸、酸雾会造成环境污染日益严重，同时酸洗及相关工序也造成生产成本高，生产效率低，另外，酸洗与热镀工序产能不匹配，不得不分几条机组生产等问题。
专利文献US6258186B1和KR100905653B1公开了一种连续生产免酸洗热轧热镀产品的方法，该工艺强调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，并且还原退火采用的氢气浓度在20％以上，锌液成分中铝含量要求在0.2-5.0wt％之间，其目标仍是不希望有氧化物层残留，即希望还原彻底，成品不含氧化物层。
发明内容
本发明的目的是针对传统热镀产品及生产工艺不足，提供一种成本低廉且耐蚀性能优良的带氧化物层的热镀产品、其制造方法及其应用，无需通过酸洗工序来去除氧化物层，而可使残留氧化物层作为一层耐蚀保护层对基板起到进一步保护作用，以延缓腐蚀。
根据本发明一方面，提供一种带氧化物层的热镀产品的制造方法，依次包括冶炼、铸造、热轧、还原退火、热浸镀步骤，所述还原退火步骤是将热轧步骤中得到的带氧化铁皮层的热轧板不经酸洗直接进入还原退火炉中，使退火炉 中的热轧板在还原性气体的保护性气氛和还原温度控制下，将其氧化铁皮的表层部分还原成金属铁,且使还原产生的金属铁存在于热轧板钢基体的最外层，形成还原铁层；将形成具有还原铁层的热轧板再经过热浸镀锌步骤后，形成带氧化物层的热镀产品。
还包括在热轧与还原退火步骤之间还增加有冷轧步骤，并将冷轧步骤中所得的带氧化铁皮的冷轧板不经酸洗直接进入还原退火炉进行还原退火。
所述的热轧步骤中，出炉温度为1100-1250℃，终轧温度为800-900℃，卷取温度为550-650℃，轧制速度为8-20m/s；所述的还原退火步骤中，还原温度为500～1000℃，停留保温时间为30s-300s，还原性气体为H2或CO与惰性气体的混合物。
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。
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17m/s或18m/s。
所述的还原温度为750-950℃，停留时间为120-300s。
所述的还原温度为800℃、850℃或900℃，停留时间为180s、240s或300s。
所述的惰性气体为N2、Ar、He中的任一种，并且H2或CO的浓度不低于3％。
所述的H2或CO的浓度为于20％-75％。
通过还原退火温度、保温时间和还原性气体浓度的控制以增加还原产生的还原铁层的厚度，使还原铁层的厚度控制在0.5μm-5μm。
根据本发明另一方面，提供一种带氧化物层的热镀产品，该热镀产品自里向外依次是钢基体、还原铁层、热浸镀层，其特征在于：该产品还包括一能够延缓钢基板腐蚀的保护层，所述的保护层位于钢基体与还原铁层之间，所述的保护层为一由氧化铁皮构成的氧化物层，所述的还原铁层为氧化铁皮的表层部分经还原退火成的金属铁所构成。
所述的氧化物层中的氧化物包含FeO、Fe3O4、Fe2O3中的任一种、两种或多种。
所述的氧化物层是连续的或者半连续的，其平均厚度在0.1-5μm。
所述的还原铁层的平均厚度为0.5-5μm。
所述热浸镀层的组成为纯Zn、Zn-Al、Zn-Al-Mg、Zn-Al-Mg-Si或Al-Si合金。
所述的热浸镀层的平均厚度在5-20μm。
根据本发明的第三方面，所述的热镀产品应用于建筑用钢、高速公路护栏用钢或仓储用钢。
本发明的有益效果是：本发明方法制造的带氧化物热镀产品，其结构自里向外依次是钢基体、保护层、还原铁层、锌层，其中保护层为本身的氧化铁皮构成，能对钢基板铁起到进一步的耐蚀防护作用，可延缓腐蚀，相比传统热镀产品，多了一道保护屏障，因此耐蚀性更强，特别适合于对耐蚀性有较高要求，同时变形程度不复杂的应用领域，如建筑用钢，高速公路护栏、仓储用钢等。除增强耐腐蚀性外，本发明省略了酸洗及相关工序，可彻底解决废酸等污染物排放问题，既节能又环保，正是大势所趋。由于免除了酸洗工序来去除氧化物层，因而可缩短生产工序、提升生产效率、提高成材率、降低生产成本。本发明方法生产的带氧化物层的热镀产品具有很强的经济性优势，同时具有很强的应用性及推广性，不涉及产线改造及新增设备，完全适用传统热镀锌产线。
附图说明
图1是传统热镀产品截面扫描电镜图；
图2是本发明的带氧化物层的热镀产品制造方法所制造的第一实施例的热镀产品截面扫描电镜图；
图3是本发明的带氧化物层的热镀产品制造方法所制造的第二实施例的热镀产品截面扫描电镜图；
图4是本发明的带氧化物层的热镀产品制造方法所制造的第三实施例的热镀产品截面扫描电镜图；
图5是本发明的带氧化物层的热镀产品制造方法所制造的第四实施例的热镀产品截面扫描电镜图。
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。
本发明的一种带氧化物层的热镀产品的制造方法，依次包括：冶炼、铸造钢板坯、热轧或冷轧钢板、还原退火、热浸镀，其中还原退火是将带氧化铁皮的热轧或冷轧板不经酸洗直接进入还原退火炉，在还原性气体的保护性气氛和一定温度控制下，将氧化铁皮的表层部分还原成金属铁,且使还原产生的金属 铁存在于最外层，形成还原铁层，剩余的氧化铁皮构成氧化物层，通过热浸镀锌或其他合金，最终形成带氧化物层的热镀产品。在具体实施方式中，热轧的出炉温度1100-1250℃，终轧温度800-900℃，卷取温度为550-650℃，轧制速度为8-20m/s，还原退火的还原温度为500～1000℃，停留时间为30s-300s，还原性气体为H2或CO与惰性气体的混合物。较佳的，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；所述的还原温度为750-950℃，停留时间为120-300s。更佳的，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17m/s或18m/s；所述的还原温度为800℃、850℃或900℃，停留时间为180s、240s或300s。所述的惰性气体为N2,Ar或He，其中H2或CO的浓度不低于3％，优选地，所述的H2或CO的浓度为于20％-75％。
通过还原退火温度、保温时间和H2浓度的综合平衡设置以增加新鲜产生的还原铁厚度，并且其平均厚度确保在0.5μm-5μm。
根据本发明的一种采用上述方法制成的带氧化物层的热镀产品，如图2所示，其自里向外依次是钢基体、保护层、还原铁层、热浸镀层，该保护层为一由还原剩余的氧化铁皮构成的氧化物层，还原铁层为氧化铁皮的表层部分经还原退火成的金属铁所构成，该保护层能够延缓钢基板的腐蚀。上述氧化物层的氧化物包含FeO、Fe3O4、Fe2O3中的一种或两种或多种，且主要是FeO。该氧化物层是连续的或者不连续的，其平均厚度在0.1-5μm。还原产生的还原铁层平均厚度为0.5-5μm。热浸镀层的平均厚度在5-20μm。热浸镀层的组成可以是纯Zn、Zn-Al、Zn-Al-Mg、Zn-Al-Mg-Si、Al-Si或其它合金。
上述制备的热镀产品可应用于建筑用钢、高速公路护栏用钢或仓储用钢。
为更清楚理解本发明的带氧化物层的热镀产品制造方法及其产品的特点、优点，以下具体说明多个实施例。
实施例1
将冶炼、铸造、除磷后的板坯进行热轧，出炉温度为1100℃，终轧温度为850℃，卷取温度为550℃，轧制速度为20m/s，热轧板最终厚度为2.2mm，氧化铁皮厚度平均6μm。进入还原退火炉，还原温度500℃，时间300s，氢气浓度3％，460℃入锌锅完成热镀锌，锌液成分0.2wt％Al-Zn，所得镀锌板的截面显微结构如图2所示，从图2可以看出，钢基板与镀锌层之间存在未还原彻底的氧化物层，而传统的传统热镀产品截面扫描电镜图无该氧化物层(见图1)。
实施例2
将冶炼、铸造、除磷后的板坯进行热轧，出炉温度为1150℃，终轧温度为870℃，卷取温度为580℃，轧制速度为15m/s，热轧板最终厚度为2.0mm，氧化铁皮厚度平均7μm。未经酸洗直接进入还原退火炉，还原温度800℃，时间180s，氢气浓度20％，460℃入锌锅完成热镀锌，锌液成分0.13wt％Al-Zn。所得镀锌板的截面显微结构如图3所示。图3显示，同样，镀锌层与钢基板之间存在一层连续的氧化物层。
实施例3
将冶炼、铸造、除磷后的板坯进行热轧，出炉温度为1200℃，终轧温度为900℃，卷取温度为600℃，轧制速度为8m/s，热轧板最终厚度为3.0mm，氧化铁皮厚度平均8μm。未经酸洗直接进入还原退火炉，还原温度1000℃，时间180s，氢气浓度50％，460℃入锌锅完成热镀锌铝镁，锌液成分1.6％Al-1.6％Mg-Zn，所得镀锌板的截面显微结构如图4所示，图4显示位置的元素分析结果见下表1，Spectrum 1代表残留氧化物层，Spectrum 2代表还原铁层，Spectrum 3代表还原铁与锌的反应产生的合金层。
表1EDS分析结果
Spectrum C O Fe Zn Total  
             
Spectrum 1   25.48 74.52   100.00  
Spectrum 2     95.88 4.12 100.00  
Spectrum 3 6.18   51.24 42.58 100.00  
数量均代表重量百分比
实施例4
将冶炼、铸造、除磷后的板坯进行热轧，出炉温度为1250℃，终轧温度为900℃，卷取温度为600℃，轧制速度为10m/s，热轧板最终厚度为3.0mm，氧化铁皮厚度平均8μm。热轧板进行带氧化皮冷轧，变形量5％，进入还原退火炉，还原温度800℃，时间60s，氢气浓度20％，460℃入锌锅完成热镀锌，锌液成分0.2％Al-Zn，所得镀锌板的截面显微结构如图5所示。
实施例5
将冶炼、铸造、除磷后的板坯进行热轧，出炉温度为1250℃，终轧温度为900℃，卷取温度为600℃，轧制速度为10m/s，热轧板最终厚度为3.0mm，氧化铁皮厚度平均8μm。热轧板进行带氧化皮冷轧，变形量5％，进入还原退火炉，还原温度800℃，时间60s，氢气浓度20％，620℃入锌锅完成热镀铝锌，锌液成分55％Al-Zn。
实施例6
将冶炼、铸造、除磷后的板坯进行热轧，出炉温度为1250℃，终轧温度为900℃，卷取温度为600℃，轧制速度为10m/s，热轧板最终厚度为3.0mm，氧化铁皮厚度平均8μm。热轧板进行带氧化皮冷轧，变形量5％，进入还原退火炉，还原温度800℃，时间60s，氢气浓度20％，680℃完成热镀铝硅，镀液成分11％Si-Al。
综上所述，本发明方法制造的带氧化物热镀产品，其结构自里向外依次是钢板、氧化物、还原铁、热浸镀层，其中氧化物本身作为一层保护层，能对基板铁起到一定的防护作用，可延缓腐蚀，相比传统热镀产品，多了一道保护屏障，因此耐蚀性更强，特别适合应用于对耐蚀性有高要求，同时变形程度不复杂的领域，如建筑用钢，高速公路护栏、仓储用钢等。并且，除了增强耐腐蚀性外，本发明还省略了酸洗及相关工序，可彻底解决废酸等污染物排放问题，既节能又环保，正是大势所趋。由于免除了酸洗工序来去除氧化物层，因而可缩短工序、提升生产效率、降低生产成本。本发明方法生产的带氧化物热镀产品具有很强的经济性优势，同时具有很强的应用性及推广性，不涉及产线改造及新增设备，完全适用传统热镀锌产线。
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 (17)

  1. 一种带氧化物层的热镀产品的制造方法，依次包括冶炼、铸造、热轧、还原退火、热浸镀步骤，其特征在于：
    所述还原退火步骤是将热轧步骤中得到的带氧化铁皮层的热轧板不经酸洗直接进入还原退火炉中，使退火炉中的热轧板在还原性气体的保护性气氛和还原温度控制下，将其氧化铁皮的表层部分还原成金属铁,且使还原产生的金属铁存在于热轧板钢基体的最外层，形成还原铁层；
    将形成具有还原铁层的热轧板再经过热浸镀锌步骤后，形成带氧化物层的热镀产品。
  2. 根据权利要求1所述的带氧化物层的热镀产品的制造方法，其特征在于：
    还包括在热轧与还原退火步骤之间还增加有冷轧步骤，并将冷轧步骤中所得的带氧化铁皮的冷轧板不经酸洗直接进入还原退火炉进行还原退火。
  3. 根据权利要求1所述的带氧化物层的热镀产品的制造方法，其特征在于：
    所述的热轧步骤中，出炉温度为1100-1250℃，终轧温度为800-900℃，卷取温度为550-650℃，轧制速度为8-20m/s；
    所述的还原退火步骤中，还原温度为500～1000℃，停留保温时间为30s-300s，还原性气体为H2或CO与惰性气体的混合物。
  4. 根据权利要求3所述的带氧化物层的热镀产品的制造方法，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。
  5. 根据权利要求3或4所述的带氧化物层的热镀产品的制造方法，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17m/s或18m/s。
  6. 根据权利要求3所述的带氧化物层的热镀产品的制造方法，其特征在于：所述的还原温度为750-950℃，停留时间为120-300s。
  7. 根据权利要求3或6所述的带氧化物层的热镀产品的制造方法，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。
  8. 根据权利要求3所述的带氧化物层的热镀产品的制造方法，其特征在于：所述的惰性气体为N2、Ar、He中的任一种，并且H2或CO的浓度不低于3％。
  9. 根据权利要求8所述的带氧化物层的热镀产品的制造方法，其特征在于：所述的H2或CO的浓度为于20％-75％。
  10. 根据权利要求7所述的带氧化物层的热镀产品的制造方法，其特征在于；通过还原退火温度、保温时间和还原性气体浓度的控制以增加还原产生的还原铁层的厚度，使还原铁层的厚度控制在0.5μm-5μm。
  11. 一种带氧化物层的热镀产品，该热镀产品自里向外依次是钢基体、还原铁层、热浸镀层，其特征在于：该产品还包括一能够延缓钢基板腐蚀的保护层，所述的保护层位于钢基体与还原铁层之间，所述的保护层为一由氧化铁皮构成的氧化物层，所述的还原铁层为氧化铁皮的表层部分经还原退火成的金属铁所构成。
  12. 根据权利要求11所述的带氧化物层的热镀产品，其特征在于:所述的氧化物层中的氧化物包含FeO、Fe3O4、Fe2O3中的任一种、两种或多种。
  13. 根据权利要求11所述的带氧化物层的热镀产品，其特征在于:所述的氧化物层是连续的或者半连续的，其平均厚度在0.1-5μm。
  14. 根据权利要求11所述的带氧化物层的热镀产品，其特征在于:所述的还原铁层的平均厚度为0.5-5μm。
  15. 根据权利要求11所述的带氧化物层的热镀产品，其特征在于:所述热浸镀层的组成为纯Zn、Zn-Al、Zn-Al-Mg、Zn-Al-Mg-Si或Al-Si合金。
  16. 根据权利要求11所述的带氧化物层的热镀产品，其特征在于：所述的热浸镀层的平均厚度在5-20μm。
  17. 一种如权利要求11～16中任一项所述的带氧化物层的热镀产品的应用，其特征在于：所述的热镀产品应用于建筑用钢、高速公路护栏用钢或仓储用钢。
PCT/CN2014/094612 2014-05-30 2014-12-23 带氧化物层的热镀产品、其制造方法及其应用 Ceased WO2015180463A1 (zh)

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