CN105200441A - Hot-dip coated product with oxide layer and its manufacturing method and use - Google Patents

Hot-dip coated product with oxide layer and its manufacturing method and use Download PDF

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Publication number
CN105200441A
CN105200441A CN201410240635.9A CN201410240635A CN105200441A CN 105200441 A CN105200441 A CN 105200441A CN 201410240635 A CN201410240635 A CN 201410240635A CN 105200441 A CN105200441 A CN 105200441A
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China
Prior art keywords
hot
hot dip
oxide skin
reduction
band
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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 CN201410240635.9A priority Critical patent/CN105200441A/en
Priority to PCT/CN2014/094612 priority patent/WO2015180463A1/en
Priority to RU2016151998A priority patent/RU2689402C2/en
Priority to JP2017514762A priority patent/JP6903572B2/en
Priority to KR1020167034951A priority patent/KR102333168B1/en
Publication of CN105200441A publication Critical patent/CN105200441A/en
Pending legal-status Critical Current

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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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Coating With Molten Metal (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Metal Rolling (AREA)

Abstract

The invention discloses a hot-dip coated product with an oxide layer and its manufacturing method and use. The manufacturing method orderly comprises melting, steel plate blank casting, cold rolling or hot rolling, reduction annealing, and zinc hot-dip coating. The reduction annealing process comprises directly feeding a steel plate into a reduction annealing furnace without pickling, and reducing the oxide surface into iron in a reduction gas protective atmosphere at a certain temperature so that the reduced iron is located on the outermost layer. After hot-dip coating, a hot-dip coated product with an oxide layer is formed. The hot-dip coated product orderly comprises a steel substrate, a protection layer, reduced iron and a hot-dip coating from inside to outside. The protection layer comprises an oxide layer. The manufacturing method is free of a pickling process for scale removal, utilizes the oxide layer as a protection layer for steel substrate protection and delays corrosion. The hot-dip coated product with an oxide layer has strong economic advantages, good applicability and generalization performance.

Description

Hot dip product with oxide skin, its manufacture method and application thereof
Technical field
The present invention relates to a kind of hot dip product and manufacture method thereof, what be specifically related to is a kind of hot dip product with oxide skin, its manufacture method and application thereof.
Background technology
Hot dip product is widely used in the industries such as automobile, household electrical appliances, building, machinofacture with its excellent solidity to corrosion; Along with the raising that market requires product corrosion resisting property, the demand of hot dip product exceedes Uncoated sheet steel gradually.
In tradition pot galvanize production process, steel plate has to pass through pickling before pot galvanize, object is removed by surface of steel plate oxide compound clean by sulfuric acid or hydrochloric acid, otherwise residual oxidization iron sheet directly can affect the wetting property of zinc liquid, and then affect tack and the continuity of hot dip product surface zinc layers.Therefore traditional hot dip product structure is that zinc layers is directly attached to steel substrate surface, interface has the Fe that is very thin 2al 5transition layer exists, and transition layer mainly plays adhesive attraction, strengthens zinc layers to the sticking power of steel plate.The subject matter that existing technique faces is that spent acid, the acid mist that pickling produces can cause environmental pollution day by day serious, pickling simultaneously and concerned process steps also cause production cost high, and production efficiency is low, in addition, pickling is not mated with hot dip operation production capacity, must not regardless of problems such as several unit productions.
Patent documentation US6258186B1 and KR100905653B1 discloses a kind of method that continuous seepage exempts from pickled hot hot dip product, this process stresses hot rolled strip batches the speed of cooling in process, to improve ferrous oxide content in oxide compound, and the density of hydrogen that reduced anneal adopts is more than 20%, in zinc liquid composition, aluminium content requirement is between 0.2-5.0wt%, its target is still does not wish that oxide skin remains, and namely wishes that reduction thoroughly, finished product oxide-free layer.
Summary of the invention
The object of the invention is for traditional hot dip product and production technique deficiency; a kind of with low cost and the hot dip product of the band oxide skin that corrosion resisting property is excellent, its manufacture method and application thereof are provided; without the need to removing oxide skin by pickling process; and residual oxidization nitride layer can be made to play further provide protection as the anti-corrosion protective layer of one deck to substrate, to delay corrosion.
According to an aspect of the present invention, a kind of manufacture method of the hot dip product with oxide skin is provided, comprise smelting, casting, hot rolling, reduced anneal, hot dip process step successively, described reduced anneal step is directly entered in reductive annealed oven without pickling by the hot-rolled sheet of the band ferric oxide cortex obtained in hot-rolled step, make the hot-rolled sheet in annealing furnace under the protective atmosphere and reduction temperature control of reducing gas, the surface part of its iron scale is reduced into metallic iron, and the metallic iron making reduction produce is present in the outermost layer of hot-rolled sheet steel matrix, form reduction iron layer; Hot-rolled sheet formation with reduction iron layer, again after galvanizing step, forms the hot dip product of band oxide skin.
Also be included in also to increase between hot rolling and reduced anneal step and have cold rolling step, and the cold-reduced sheet of the band iron scale of gained in cold rolling step is directly entered reductive annealed oven without pickling carry out reduced anneal.
In described hot-rolled step, tapping temperature is 1100-1250 DEG C, and finishing temperature is 800-900 DEG C, and coiling temperature is 550-650 DEG C, and roll speed is 8-20m/s; In described reduced anneal step, reduction temperature is 500 ~ 1000 DEG C, and stop soaking time is 30s-300s, and reducing gas is H 2or the mixture of CO and rare gas element.
Described tapping temperature is 1150-1200 DEG C, and finishing temperature is 840-870 DEG C, and coiling temperature is 550-570 DEG C, and roll speed is 14-18m/s.
Described tapping temperature is 1170 DEG C or 1200 DEG C, and finishing temperature is 850 DEG C or 860 DEG C, and coiling temperature is 550 DEG C or 560 DEG C, and roll speed is 17m/s or 18m/s.
Described reduction temperature is 750-950 DEG C, and the residence time is 120-300s.
Described reduction temperature is 800 DEG C, 850 DEG C or 900 DEG C, and the residence time is 180s, 240s or 300s.
Described rare gas element is N 2, any one in Ar, He, and H 2or the concentration of CO is not less than 3%.
The concentration of described H2 or CO is in 20%-75%.
By the control of reduced anneal temperature, soaking time and reducing gas concentration with the thickness of the reduction iron layer increasing reduction and produce, make the gauge control of reduction iron layer at 0.5 μm-5 μm.
According to a further aspect of the invention; a kind of hot dip product with oxide skin is provided; this hot dip product from inner be outwards steel matrix, reduction iron layer, hot-dip coated successively; it is characterized in that: this product also comprises the protective layer that can delay steel substrate corrosion; described protective layer is between steel matrix and reduction iron layer; described protective layer is an oxide skin be made up of iron scale, and the metallic iron that the surface part that described reduction iron layer is iron scale becomes through reduced anneal is formed.
Oxide compound in described oxide skin comprises FeO, Fe 3o 4, Fe 2o 3in any one, two or more.
Described oxide skin is continuous print or semi-continuous, and its mean thickness is at 0.1-5 μm.
The mean thickness of described reduction iron layer is 0.5-5 μm.
Describedly hot-dip coated consist of pure Zn, Zn-Al, Zn-Al-Mg, Zn-Al-Mg-Si or Al-Si alloy.
Described hot-dip coated mean thickness is at 5-20 μm.
According to a third aspect of the invention we, described hot dip product application is in construction(al)steel, freeway guardrail steel or storage steel.
The invention has the beneficial effects as follows: the band oxide compound hot dip product that the inventive method manufactures; its structure from inner be outwards steel matrix, protective layer, reduction iron layer, zinc layers successively; wherein protective layer is the iron scale formation of itself; further anti-corrosion protective effect can be played to steel substrate iron; corrosion can be delayed; compare traditional hot dip product; many one protective barriers; therefore solidity to corrosion is stronger; be particularly suitable for having higher requirements to solidity to corrosion; the uncomplicated Application Areas of deformation extent simultaneously, as construction(al)steel, freeway guardrail, storage steel etc.Except enhancing erosion resistance, present invention omits pickling and concerned process steps, thoroughly can solve the pollutant emission problems such as spent acid, not only energy-conservation but also environmental protection, just trend of the times.Remove oxide skin owing to eliminating pickling process, thus can shorten production process, improving production efficiency, raising lumber recovery, reduce production cost.The hot dip product of the band oxide skin that the inventive method is produced has very strong economy advantage, has very strong applicability and generalization simultaneously, does not relate to and produces line transformation and newly added equipment, is suitable for traditional pot galvanize completely and produces line.
Accompanying drawing explanation
Fig. 1 is traditional hot dip product cross section scanning electron microscope (SEM) photograph;
Fig. 2 is the hot dip product cross section scanning electron microscope (SEM) photograph of first embodiment manufactured by hot dip Manufacturing Method of Products of band oxide skin of the present invention;
Fig. 3 is the hot dip product cross section scanning electron microscope (SEM) photograph of second embodiment manufactured by hot dip Manufacturing Method of Products of band oxide skin of the present invention;
Fig. 4 is the hot dip product cross section scanning electron microscope (SEM) photograph of the 3rd embodiment manufactured by hot dip Manufacturing Method of Products of band oxide skin of the present invention;
Fig. 5 is the hot dip product cross section scanning electron microscope (SEM) photograph of the 4th embodiment manufactured by hot dip Manufacturing Method of Products of band oxide skin of the present invention.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent, below in conjunction with accompanying drawing, the specific embodiment of the present invention is elaborated.First it should be noted that, the present invention is not limited to following embodiment, and the spirit that those skilled in the art should embody from following embodiment is to understand the present invention, and each technical term can do the most wide in range understanding based on spirit of the present invention.
The manufacture method of a kind of hot dip product with oxide skin of the present invention, comprise successively: smelt, cast steel slab, hot rolling or cold-rolled steel sheet, reduced anneal, hot dip process, wherein reduced anneal is that the hot rolling of band iron scale or cold-reduced sheet are directly entered reductive annealed oven without pickling, under the protective atmosphere and certain temperature control of reducing gas, the surface part of iron scale is reduced into metallic iron, and the metallic iron making reduction produce is present in outermost layer, form reduction iron layer, remaining iron scale forms oxide skin, by galvanizing or other alloys, the final hot dip product forming band oxide skin.In a specific embodiment, the tapping temperature 1100-1250 DEG C of hot rolling, finishing temperature 800-900 DEG C, coiling temperature is 550-650 DEG C, and roll speed is 8-20m/s, and the reduction temperature of reduced anneal is 500 ~ 1000 DEG C, the residence time is 30s-300s, and reducing gas is H 2or the mixture of CO and rare gas element.Preferably, described tapping temperature is 1150-1200 DEG C, and finishing temperature is 840-870 DEG C, and coiling temperature is 550-570 DEG C, and roll speed is 14-18m/s; Described reduction temperature is 750-950 DEG C, and the residence time is 120-300s.Better, described tapping temperature is 1170 DEG C or 1200 DEG C, and finishing temperature is 850 DEG C or 860 DEG C, and coiling temperature is 550 DEG C or 560 DEG C, and roll speed is 17m/s or 18m/s; Described reduction temperature is 800 DEG C, 850 DEG C or 900 DEG C, and the residence time is 180s, 240s or 300s.Described rare gas element is N 2, Ar or He, wherein H 2or the concentration of CO is not less than 3%, preferably, described H 2or the concentration of CO is in 20%-75%.
By reduced anneal temperature, soaking time and H 2the overall equilbrium of concentration is arranged with the reduced iron thickness increasing fresh generation, and its mean thickness is guaranteed at 0.5 μm-5 μm.
According to the hot dip product of a kind of band oxide skin adopting aforesaid method to make of the present invention; as shown in Figure 2; its from inner be outwards steel matrix, protective layer, reduction iron layer, hot-dip coated successively; this protective layer is an oxide skin be made up of the remaining iron scale of reduction; the metallic iron that the surface part that reduction iron layer is iron scale becomes through reduced anneal is formed, and this protective layer can delay the corrosion of steel substrate.The oxide compound of above-mentioned oxide skin comprises FeO, Fe 3o 4, Fe 2o 3in one or two or more, and mainly FeO.This oxide skin is continuous print or discontinuous, and its mean thickness is at 0.1-5 μm.The reduction iron layer mean thickness that reduction produces is 0.5-5 μm.Hot-dip coated mean thickness is at 5-20 μm.Hot-dip coated composition can be pure Zn, Zn-Al, Zn-Al-Mg, Zn-Al-Mg-Si, Al-Si or other alloy.
The hot dip product of above-mentioned preparation can be applicable to construction(al)steel, freeway guardrail steel or storage steel.
For feature, the advantage of the hot dip Manufacturing Method of Products and products thereof of clearer understanding band oxide skin of the present invention, below illustrate multiple embodiment.
Embodiment 1
Slab after smelting, casting, dephosphorization is carried out hot rolling, and tapping temperature is 1100 DEG C, and finishing temperature is 850 DEG C, and coiling temperature is 550 DEG C, and roll speed is 20m/s, and hot-rolled sheet final thickness is 2.2mm, average 6 μm of iron scale thickness.Enter reductive annealed oven, reduction temperature 500 DEG C, time 300s, density of hydrogen 3%, 460 DEG C enter zinc pot and complete pot galvanize, zinc liquid composition 0.2wt%Al-Zn, the cross section microstructure of gained galvanized sheet as shown in Figure 2, as can be seen from Figure 2, exist between steel substrate and zinc coating and do not reduce oxide skin thoroughly, and traditional traditional hot dip product cross section scanning electron microscope (SEM) photograph is without this oxide skin (see Fig. 1).
Embodiment 2
Slab after smelting, casting, dephosphorization is carried out hot rolling, and tapping temperature is 1150 DEG C, and finishing temperature is 870 DEG C, and coiling temperature is 580 DEG C, and roll speed is 15m/s, and hot-rolled sheet final thickness is 2.0mm, average 7 μm of iron scale thickness.Directly enter reductive annealed oven without pickling, reduction temperature 800 DEG C, time 180s, density of hydrogen 20%, 460 DEG C enter zinc pot and complete pot galvanize, zinc liquid composition 0.13wt%Al-Zn.The cross section microstructure of gained galvanized sheet as shown in Figure 3.Fig. 3 shows, and equally, there is one deck continuous print oxide skin between zinc coating and steel substrate.
Embodiment 3
Slab after smelting, casting, dephosphorization is carried out hot rolling, and tapping temperature is 1200 DEG C, and finishing temperature is 900 DEG C, and coiling temperature is 600 DEG C, and roll speed is 8m/s, and hot-rolled sheet final thickness is 3.0mm, average 8 μm of iron scale thickness.Directly reductive annealed oven is entered without pickling, reduction temperature 1000 DEG C, time 180s, density of hydrogen 50%, 460 DEG C enter zinc pot and complete pot galvanize magnalium, zinc liquid composition 1.6%Al-1.6%Mg-Zn, as shown in Figure 4, the results of elemental analyses of Fig. 4 display position 1, the Spectrum1 that sees the following form represents residual oxidization nitride layer to the cross section microstructure of gained galvanized sheet, Spectrum2 representative reduction iron layer, the alloy layer that the reaction that Spectrum3 represents reduced iron and zinc produces.
Table 1EDS analytical results
Spectrum C O Fe Zn Total
Spectrum1 25.48 74.52 100.00
Spectrum2 95.88 4.12 100.00
Spectrum3 6.18 51.24 42.58 100.00
Quantity all represents weight percent
Embodiment 4
Slab after smelting, casting, dephosphorization is carried out hot rolling, and tapping temperature is 1250 DEG C, and finishing temperature is 900 DEG C, and coiling temperature is 600 DEG C, and roll speed is 10m/s, and hot-rolled sheet final thickness is 3.0mm, average 8 μm of iron scale thickness.It is cold rolling that hot-rolled sheet carries out band oxide skin, and deflection 5%, enters reductive annealed oven, reduction temperature 800 DEG C, time 60s, density of hydrogen 20%, and 460 DEG C enter zinc pot and complete pot galvanize, and zinc liquid composition 0.2%Al-Zn, the cross section microstructure of gained galvanized sheet as shown in Figure 5.
Embodiment 5
Slab after smelting, casting, dephosphorization is carried out hot rolling, and tapping temperature is 1250 DEG C, and finishing temperature is 900 DEG C, and coiling temperature is 600 DEG C, and roll speed is 10m/s, and hot-rolled sheet final thickness is 3.0mm, average 8 μm of iron scale thickness.It is cold rolling that hot-rolled sheet carries out band oxide skin, and deflection 5%, enters reductive annealed oven, reduction temperature 800 DEG C, time 60s, density of hydrogen 20%, and 620 DEG C enter zinc pot and complete hot-dip aluminizing zinc, zinc liquid composition 55%Al-Zn.
Embodiment 6
Slab after smelting, casting, dephosphorization is carried out hot rolling, and tapping temperature is 1250 DEG C, and finishing temperature is 900 DEG C, and coiling temperature is 600 DEG C, and roll speed is 10m/s, and hot-rolled sheet final thickness is 3.0mm, average 8 μm of iron scale thickness.It is cold rolling that hot-rolled sheet carries out band oxide skin, and deflection 5%, enters reductive annealed oven, reduction temperature 800 DEG C, time 60s, density of hydrogen 20%, and 680 DEG C complete hot-dip aluminizing silicon, solution composition 11%Si-Al.
In sum; the band oxide compound hot dip product that the inventive method manufactures; its structure from inner be outwards steel plate, oxide compound, reduced iron, hot-dip coated successively; wherein oxide compound itself is as layer protective layer; certain protective effect can be played to substrate iron; corrosion can be delayed; compare traditional hot dip product; many one protective barriers; therefore solidity to corrosion is stronger, is particularly suitable for and has high request to solidity to corrosion, simultaneously the uncomplicated field of deformation extent; as construction(al)steel, freeway guardrail, storage steel etc.Further, except strengthening except erosion resistance, the present invention is omitted pickling and concerned process steps, thoroughly can solve the pollutant emission problems such as spent acid, not only energy-conservation but also environmental protection, just trend of the times.Remove oxide skin owing to eliminating pickling process, thus can shorten operation, improving production efficiency, reduction production cost.The band oxide compound hot dip product that the inventive method is produced has very strong economy advantage, has very strong applicability and generalization simultaneously, does not relate to and produces line transformation and newly added equipment, is suitable for traditional pot galvanize completely and produces line.
Should be understood that those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.

Claims (17)

1. a manufacture method for the hot dip product with oxide skin, comprises smelting, casting, hot rolling, reduced anneal, hot dip process step successively, it is characterized in that:
Described reduced anneal step is directly entered in reductive annealed oven without pickling by the hot-rolled sheet of the band ferric oxide cortex obtained in hot-rolled step, make the hot-rolled sheet in annealing furnace under the protective atmosphere and reduction temperature control of reducing gas, the surface part of its iron scale is reduced into metallic iron, and the metallic iron making reduction produce is present in the outermost layer of hot-rolled sheet steel matrix, form reduction iron layer;
Hot-rolled sheet formation with reduction iron layer, again after galvanizing step, forms the hot dip product of band oxide skin.
2. the manufacture method of the hot dip product of band oxide skin according to claim 1, is characterized in that:
Also be included in also to increase between hot rolling and reduced anneal step and have cold rolling step, and the cold-reduced sheet of the band iron scale of gained in cold rolling step is directly entered reductive annealed oven without pickling carry out reduced anneal.
3. the manufacture method of the hot dip product of band oxide skin according to claim 1, is characterized in that:
In described hot-rolled step, tapping temperature is 1100-1250 DEG C, and finishing temperature is 800-900 DEG C, and coiling temperature is 550-650 DEG C, and roll speed is 8-20m/s;
In described reduced anneal step, reduction temperature is 500 ~ 1000 DEG C, and stop soaking time is 30s-300s, and reducing gas is H 2or the mixture of CO and rare gas element.
4. the manufacture method of the hot dip product of band oxide skin according to claim 3, is characterized in that: described tapping temperature is 1150-1200 DEG C, and finishing temperature is 840-870 DEG C, and coiling temperature is 550-570 DEG C, and roll speed is 14-18m/s.
5. the manufacture method of the hot dip product of the band oxide skin according to claim 3 or 4, it is characterized in that: described tapping temperature is 1170 DEG C or 1200 DEG C, finishing temperature is 850 DEG C or 860 DEG C, and coiling temperature is 550 DEG C or 560 DEG C, and roll speed is 17m/s or 18m/s.
6. the manufacture method of the hot dip product of band oxide skin according to claim 3, is characterized in that: described reduction temperature is 750-950 DEG C, and the residence time is 120-300s.
7. the manufacture method of the hot dip product of the band oxide skin according to claim 3 or 6, is characterized in that: described reduction temperature is 800 DEG C, 850 DEG C or 900 DEG C, and the residence time is 180s, 240s or 300s.
8. the manufacture method of the hot dip product of band oxide skin according to claim 3, is characterized in that: described rare gas element is N 2, any one in Ar, He, and H 2or the concentration of CO is not less than 3%.
9. the manufacture method of the hot dip product of band oxide skin according to claim 8, is characterized in that: described H 2or the concentration of CO is in 20%-75%.
10. the manufacture method of the hot dip product of band oxide skin according to claim 7, is characterized in that; By the control of reduced anneal temperature, soaking time and reducing gas concentration with the thickness of the reduction iron layer increasing reduction and produce, make the gauge control of reduction iron layer at 0.5 μm-5 μm.
11. 1 kinds of hot dip products with oxide skin; this hot dip product from inner be outwards steel matrix, reduction iron layer, hot-dip coated successively; it is characterized in that: this product also comprises the protective layer that can delay steel substrate corrosion; described protective layer is between steel matrix and reduction iron layer; described protective layer is an oxide skin be made up of iron scale, and the metallic iron that the surface part that described reduction iron layer is iron scale becomes through reduced anneal is formed.
The hot dip product of 12. band oxide skins according to claim 11, is characterized in that: the oxide compound in described oxide skin comprises FeO, Fe 3o 4, Fe 2o 3in any one, two or more.
The hot dip product of 13. band oxide skins according to claim 11, is characterized in that: described oxide skin is continuous print or semi-continuous, and its mean thickness is at 0.1-5 μm.
The hot dip product of 14. band oxide skins according to claim 11, is characterized in that: the mean thickness of described reduction iron layer is 0.5-5 μm.
The hot dip product of 15. band oxide skins according to claim 11, is characterized in that: describedly hot-dip coated consist of pure Zn, Zn-Al, Zn-Al-Mg, Zn-Al-Mg-Si or Al-Si alloy.
The hot dip product of 16. band oxide skins according to claim 11, is characterized in that: described hot-dip coated mean thickness is at 5-20 μm.
The application of the hot dip product of 17. 1 kinds of band oxide skins according to any one of claim 11 ~ 16, is characterized in that: described hot dip product application is in construction(al)steel, freeway guardrail steel or storage steel.
CN201410240635.9A 2014-05-30 2014-05-30 Hot-dip coated product with oxide layer and its manufacturing method and use Pending CN105200441A (en)

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