WO1993016210A1 - TOLE D'ACIER PLAQUEE Al-Si-Cr, AYANT UNE EXCELLENTE RESISTANCE A LA CORROSION, ET PRODUCTION DE CETTE TOLE - Google Patents

TOLE D'ACIER PLAQUEE Al-Si-Cr, AYANT UNE EXCELLENTE RESISTANCE A LA CORROSION, ET PRODUCTION DE CETTE TOLE Download PDF

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Publication number
WO1993016210A1
WO1993016210A1 PCT/JP1993/000163 JP9300163W WO9316210A1 WO 1993016210 A1 WO1993016210 A1 WO 1993016210A1 JP 9300163 W JP9300163 W JP 9300163W WO 9316210 A1 WO9316210 A1 WO 9316210A1
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WIPO (PCT)
Prior art keywords
layer
plating
steel
alloy
steel sheet
Prior art date
Application number
PCT/JP1993/000163
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English (en)
French (fr)
Japanese (ja)
Inventor
Yasushi Fukui
Tadaaki Miono
Minoru Saito
Original Assignee
Nisshin Steel Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP4059017A external-priority patent/JPH05222519A/ja
Priority claimed from JP4059016A external-priority patent/JP2938658B2/ja
Priority claimed from JP5034759A external-priority patent/JPH06228725A/ja
Priority claimed from JP03476093A external-priority patent/JP3207958B2/ja
Application filed by Nisshin Steel Co., Ltd. filed Critical Nisshin Steel Co., Ltd.
Priority to KR1019930703118A priority Critical patent/KR0166099B1/ko
Priority to DE69305458T priority patent/DE69305458T2/de
Priority to EP93903330A priority patent/EP0584364B1/de
Priority to CA002107560A priority patent/CA2107560C/en
Publication of WO1993016210A1 publication Critical patent/WO1993016210A1/ja

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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
    • C23C2/04—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
    • C23C2/003—Apparatus
    • C23C2/0034—Details related to elements immersed in bath
    • 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
    • C23C2/003—Apparatus
    • C23C2/0034—Details related to elements immersed in bath
    • C23C2/00342—Moving elements, e.g. pumps or mixers
    • C23C2/00344—Means for moving substrates, e.g. immersed rollers or immersed bearings
    • 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
    • C23C2/003—Apparatus
    • C23C2/0035—Means for continuously moving substrate through, into or out of the bath
    • 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
    • C23C2/003—Apparatus
    • C23C2/0038—Apparatus characterised by the pre-treatment chambers located immediately upstream of the bath or occurring locally before the dipping process
    • 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
    • C23C2/003—Apparatus
    • C23C2/0038—Apparatus characterised by the pre-treatment chambers located immediately upstream of the bath or occurring locally before the dipping process
    • C23C2/004—Snouts
    • 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
    • C23C2/024—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
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C23C2/026—Deposition of sublayers, e.g. adhesion layers or pre-applied alloying elements or corrosion protection

Definitions

  • the present invention relates to a fusion-coated steel sheet whose corrosion resistance and heat resistance are remarkably improved by adding Cr to an A1-Si-based fusion-coated layer and a method for producing the same.
  • a 1 -Si-based alloy-coated steel sheets are manufactured by a hot-dip plating method in which the steel sheets are immersed in a hot-dip bath containing A 1 and Si.
  • the A 1 -Si alloy coating layer formed on the surface of the steel sheet has excellent corrosion resistance and heat resistance and has a beautiful surface appearance, so it is used in a wide range of fields as automotive exhaust system materials, building materials, etc. Have been.
  • the hot-dip A 1 -Si alloy plating method continuous hot-dip plating equipment with an in-line reduction method is usually used.
  • the steel sheet surface is activated by gas cleaning that reduces and removes the oxide film from the steel sheet surface by annealing the original plate under a reducing atmosphere in the pretreatment zone. Since the surface is activated, the original plate is then introduced into a molten A 1 -Si alloy plating bath.
  • the use of an A1-Si alloy plating bath containing Cr allows the A1-Si alloy-coated steel sheet to have a thickness of 0.1%.
  • the inclusion of Cr in an amount of 0 to 2% by weight is introduced in Japanese Patent Application Laid-Open No. 2-878754.
  • the resulting plated steel sheet is used as a structural material that exhibits sufficient durability even in a severe atmosphere.
  • the amount of Cr that can be added is restricted.
  • the molten A 1 -S ⁇ alloy plating bath used in ordinary fusion plating lines has a Si content of 18% by weight or less and is maintained at a bath temperature of 680 ° C or less. Is done.
  • the content of Cr added to the A1-Si alloy plating bath is regulated to 0.5% by weight or less.
  • the Cr content of the A1-Si alloy-coated layer is restricted, and the corrosion resistance of the obtained A1-Si-coated steel sheet cannot be significantly improved.
  • a 1 As a method to further increase the corrosion resistance of Si-based alloy-coated steel sheets, Cr-containing low alloy steels, stainless steels, etc., which themselves have excellent corrosion resistance, are used as plating base plates instead of ordinary steel. .
  • the raw material cost and production cost of the plated steel sheet are high, and the A 1—Si alloy is plated.
  • the product cost of the steel sheet as a whole increases.
  • stainless steel containing 16% by weight or more of Cr was used as the plating original plate
  • ordinary steel such as A1 killed steel and low carbon steel plate were used as the plating original plate.
  • the product price is more than doubled compared to the case. For this reason, it is necessary to use steel that does not contain Cr or low-grade stainless steel that has a low Cr content as the original plate, and it is not possible to expect a significant improvement in corrosion resistance.
  • the oxide film on the steel sheet surface is removed with a reducing gas.
  • the ordinary in-line reduction method is designed for melting and coating of ordinary steel, and is an alloy steel containing an easily oxidizable element that is easily oxidized and an oxide film is easily formed on the steel sheet surface. Not suitable for steel plates such as stainless steel.
  • Japanese Patent Publication No. 63-444825 discloses that after plating Ni, Cu, Co, Cr, etc. It is introduced that hot-dip A1 plating using the gas-cleaning method can provide A1-plated steel sheets with excellent corrosion resistance.
  • a strong oxide film is also formed on the surface of the steel sheet, even in the Cr coated original sheet. Therefore, the surface of the steel sheet having the Cr oxide film is formed in a reducing gas atmosphere such as ⁇ 2 , H 2 + N 2 , in the range of 500 to 850. Under normal conditions of heating to the temperature of C, the reduction reaction of the oxide film does not proceed thermodynamically. For example, even if the Cr coated steel sheet is heated to 700 ° C for 5 minutes in a H 2 + 25% N 2 reducing gas atmosphere with a dew point of 16 CTC, the oxide film is not removed from the steel sheet surface.
  • a reducing gas atmosphere such as ⁇ 2 , H 2 + N 2
  • the reaction between the underlying steel and the plating layer is partial even in the area where the plating is attached, and most of the plating layer simply rides on the Cr-coated steel sheet by physical force. Not just. Therefore, the formed plating layer has poor adhesion and easily peels off from the steel sheet surface by light processing. Therefore, even where the plating layer is attached, it cannot withstand actual use.
  • the oxide film When the oxide film is completely removed from the surface of the steel sheet, the reaction between the base steel and the plating layer progresses, and it is expected that defects such as non-plating and poor adhesion are suppressed.
  • high-temperature heating is required to quickly remove the oxide film by the gas reduction method (gas cleaning method).
  • gas reduction method gas cleaning method
  • the oxide film is first removed at an atmosphere temperature exceeding 100 ° C.
  • most steel types cannot be heated at high temperatures because they deteriorate mechanical properties such as elongation and strength.
  • Japanese Patent Publication No. 63-44825 discloses that an A 1 bath containing only an impurity of Si is used. i
  • the temperature of the plating bath is maintained at 700 ° C. higher than the temperature of the alloy plating bath of 62 ° to 70 ° C. Limiting the S i content and increasing the temperature of the plating bath are effective in increasing the reactivity of the plating bath and reducing the area ratio of non-plating. However, even with this method, the occurrence of non-plating cannot be completely suppressed.
  • the adhesion of the A 1 -S i alloy plating layer to the base steel is determined in advance by the plating base plate. Fe, Fe alloy, etc. It is improved by replating.
  • the pre-plated plate is passed through a usual in-line reduction annealing continuous melting plating equipment, the oxide film is easily reduced and removed from the steel plate surface.
  • the Fe or Fe alloy-based plating layer is applied to the plating layer when the molten plating layer is not solidified. melting out. As a result, the Fe concentration in the plating layer increases, and the resulting steel sheet has a reduced corrosion resistance.
  • the present invention has been devised to solve such a problem. It is intended to melt a steel sheet having a Cr coating layer in an active state where an oxide film is not formed.
  • the first objective is to produce a plated steel sheet with a sound A 1 -Si i-Cr based coating layer without non-plating and poor adhesion by introducing it into the plating bath.
  • the second objective is to improve the layer structure of the plating layer by manipulating the manufacturing conditions, and to obtain an A1-Si1-Cr-based steel sheet with dramatically improved corrosion resistance and heat resistance. I do.
  • the plating original plate on which the Cr coating layer having a surface in a neutral state is formed is introduced into a molten A1-Si alloy plating bath.
  • the Cr coating layer is formed on the surface of the original plate by electroplating or vacuum deposition.
  • the following methods can be used to introduce a Cr-coated steel sheet with its active surface maintained into a molten A1-Si-based alloy plating bath.
  • the plasma-etched or ion-beam etched Cr coated steel sheet is introduced into the A1-Si based alloy plating bath while maintaining the activated surface state without an oxide film. Therefore, a healthy plating layer grows on the steel sheet surface without the reaction between the F ground steel and the plating layer being hindered by the Cr oxide film.
  • the Cr coating is formed by vapor deposition in a vacuum atmosphere or by electro-charging in an air atmosphere. After the formation of the Cr coating, the fusion plating may be performed immediately, or the plating original plate may be stored, and the molten A1-Si-based alloy may be plated according to the production plan.
  • the plasma etching activated melting plating apparatus and the ion beam etching activated melting plating apparatus are maintained in a vacuum atmosphere. Therefore, when Cr is deposited on a plating base plate that has been subjected to plasma etching activation treatment or ion beam etching activation treatment using this space, it is more inexpensive to melt the A1-Si-Cr system. Steel sheet is manufactured. In addition, a high-purity Cr coating layer is formed at low cost and with high productivity.
  • the Cr coating layer is formed on the surface of the original plate by electroplating, vacuum evaporation, or other methods. Cr coating layer can be obtained plating! ] From the viewpoint of improving the corrosion resistance of the plate, it is preferable to have a thickness of 0.02 m or more.
  • the Cr coating layer diffuses into the formed plating layer when the plating base plate is introduced into the molten A1-Si alloy plating bath. When the Cr coating layer is thick, the Cr coating layer remains between the base steel and the plating layer of the obtained plated steel sheet. When a thin Cr coating layer is formed, the Cr coating layer diffuses into the plating layer when the plating layer is formed, and no Cr layer remains at the interface between the base steel and the plating layer.
  • the Cr coating layer remains at the interface between the base steel and the plating layer r In addition to the thickness of the coating layer, it is affected by the temperature, composition, and immersion time of the bath for the molten A1-Si alloy. In any case, since the plating layer containing Cr is formed, the corrosion resistance is greatly improved. When a plating layer including a layer having a Cr concentration of 0.7% by weight or more is formed in a part of the plating layer, the corrosion resistance of the resulting plated steel sheet is significantly improved. In addition, since the plating reaction is performed via the Cr coating layer having an active surface, the formed plating layer has no defects such as non-plating and has excellent adhesion to the base steel. In addition, the Cr coating layer has the effect of suppressing the diffusion of Fe from the base steel, and ensures the corrosion resistance and workability of the plating layer itself.
  • the Cr coating layer at the interface controls the alloying reaction between the base steel and the plating layer, making it brittle. No thick alloy layer is formed. As a result, the obtained plated steel sheet becomes a product having excellent workability.
  • the temperature of the plating bath is set to a high value or when the immersion time is lengthened, a large amount of Cr diffuses into the plating layer, and Cr-Si-A1 alloy particles precipitate. . Precipitation of Cr-Si-A1-based alloy particles is very effective in improving the corrosion resistance of plated steel sheets.
  • a Cr coating layer having a thickness of 0.1 im or more on the surface of the original plate.
  • the molten A1-Si alloy plating bath used in the present invention is not subject to any particular restrictions on the composition and temperature, but it can extend the life of the plating bath pot and melt the good surface appearance.
  • the S i concentration is maintained in the range of 1 to 13% by weight, and the bath temperature is maintained at a temperature of 680 ° C. or lower.
  • the Si concentration is maintained at 6 to 12% by weight and the bath temperature at 680 ° C or lower.
  • the molten A 1—Si alloy plating bath can also contain Cr as the third component.
  • the amount of Cr added to the plating bath is not particularly limited, but is practically limited to 0.5% by weight. If excessive Cr is contained, the melting point of the A1-Si-based alloy increases, and it is necessary to maintain the plating bath at a high temperature.
  • the molten A1-Si alloy plating bath contains, as impurities, component elements dissolved from the plating bath and the heat-resistant steel of the bath.
  • impurities Fe is the element with the highest content, but the Fe concentration is usually regulated to 3% by weight or less. If a plating bath containing a large amount of Fe is used, if the Cr coating layer remains, a part of the plating layer formed on the steel sheet surface will incorporate A 1— An Si-Cr-Fe alloy layer is formed.
  • the elution of Fe from the plating bath pot into the plating bath can be suppressed by using a pot lined with ceramics or the like. Since the plating original plate to be used is also coated with Cr, elution of Fe from the plating original plate into the plating bath is also suppressed. Therefore, the Fe concentration of the plating bath is kept very low, and the plating layer formed on the steel sheet surface has a low Fe concentration.
  • the plating base sheet is not subject to any particular restrictions on its material.
  • ordinary steel such as A1 killed steel is used. Even if inexpensive ordinary steel is used as the original plate, a plated steel plate exhibiting corrosion resistance comparable to high-grade steel plates such as stainless steel can be obtained.
  • low alloy steel, stainless steel, etc. are used.
  • low alloy steel, low grade stainless steel, etc. is used as the original plate, the corrosion resistance and heat resistance surpass those of high Cr high Ni stainless steel due to the melting of the Cr coated A1-Si alloy.
  • a plated steel sheet exhibiting the properties is obtained.
  • FIG. 1 shows an equipment configuration for continuously performing plasma etching, Cr evaporation and hot-dip plating in the same vacuum atmosphere according to the present invention.
  • Fig. 2 shows the equipment configuration for continuously performing ion beam etching, Cr evaporation and melting in the same vacuum atmosphere.
  • Fig. 3 shows the equipment configuration for continuously performing Cr evaporation, plasma etching, and melting in the same vacuum atmosphere.
  • Fig. 4 shows the equipment configuration for continuously performing Cr evaporation, ion beam etching, and melting in the same vacuum atmosphere.
  • FIG. 5 shows a layer configuration of a plating layer obtained according to the present invention.
  • FIG. 6 shows the layer configuration of the plating layer when the Cr concentration is high.
  • Fig. 7 is a graph showing the effect of the thickness of the Cr coating layer on the Cr concentration of the second layer of the glazed layer formed in Example 1 and the corrosion resistance of the plated steel sheet.
  • Fig. 8 shows a plating layer on which Si litz alloy particles were precipitated.
  • Fig. 9 is a graph showing the effect of the thickness of the Cr coating layer on the Cr concentration of the second layer of the glazed layer formed in Example 2 and the corrosion resistance of the plated steel sheet.
  • FIG. 10 is a graph showing the effect of the thickness of the Cr coating layer on the Cr concentration of the second layer of the plating layer formed in Example 3 and the corrosion resistance of the plated steel sheet.
  • FIG. 11 shows the structure and concentration of the welded layer formed on the surface of the fusion-plated steel sheet in Example 5.
  • FIG. 12 is a graph showing the corrosion resistance of the plated steel sheet obtained in Example 5 in relation to the thickness of the Cr coating layer.
  • FIG. 13 is a graph showing the corrosion resistance of molten A1-Si alloys after electroplating compared to Fe-plated ones.
  • FIG. 14 is a graph showing the effect of the thickness of the Cr coating layer and the temperature of the plating bath on the corrosion resistance of the plated steel sheet obtained in Example 6.
  • a Cr coated steel sheet in which the surface of the Cr coated layer is kept active is introduced into a molten A1-Si alloy plating bath.
  • the Cr coating layer is formed by electroplating or vacuum evaporation.
  • the surface activation of the Cr coating layer is performed by plasma etching, ion beam etching, or the like.
  • the activity of the Cr coating layer can be increased. Contact between the surface and the bath is made.
  • the original plate is activated by plasma etching, ion beam etching, etc. to improve the adhesion of the Cr coating layer formed by vapor deposition to the underlying steel. I do.
  • the present invention is carried out according to the following various steps.
  • a melting plating facility is constructed.
  • FIG. 1 shows equipment in which various devices are arranged in accordance with the process described above.
  • the original plating plate 10 is sent out from the pay-off reel 11, guided by the deflector rolls 12 and 13, and sent into the vacuum chamber 20.
  • a vacuum seal device 21 is provided on the entrance side of the vacuum tank 20, and a high-frequency heating device 30, a Cr vapor deposition device 40, and a plasma etching device 50 are provided along the traveling direction of the original plating plate 10. Are arranged.
  • the outlet side of the vacuum chamber 20 is vacuum-sealed by being immersed in the melting plating bath 61 of the melting plating apparatus S0. At this time, the melting plating bath 61 is sucked up from the plating pot 62 in accordance with the degree of vacuum in the vacuum chamber 20, and a snout portion 63 is formed. Therefore, the outlet side of the vacuum chamber 20 is completely vacuum-sealed by the melting plating bath 61.
  • the vacuum chamber 20 is evacuated by vacuum pumps 22 and 23.
  • the original plate 10 introduced into the vacuum chamber 20 is heated to a predetermined temperature by the high-frequency heating device 30, and then coated with Cr by the Cr vapor deposition device 40.
  • the surface is activated by the plasma etching apparatus 50.
  • the original plating plate 10 is introduced into the plating bath 61 through the snout portion 63.
  • the original plating plate 10 is conveyed through the sink rolls 64 and 65 in the plating bath 61, lifted from the plating bath 61, and the amount of plating applied is adjusted by the gas wiping device 66.
  • the plated steel sheet is taken up on a take-up reel 17 via deflector rolls 14 to 16.
  • Fig. 2 shows a layout in which various devices are arranged according to the process (1).
  • a pair of ion beam etching apparatuses 70 and 70 are mounted on both sides of an original plate 10 running in a vacuum chamber 20. Are placed.
  • the ion beams 71 and 71 emitted from the ion beam etching devices 70 and 70 collide with the surface of the original plating plate 10 and strike the surface of the Cr coating layer formed by the Cr vapor deposition device 40. A certain oxide film or surface altered layer is removed by etching.
  • the Cr coating layer is formed by the Cr vapor deposition device 40 maintained in the same vacuum atmosphere as the fusion plating device 60. Therefore, the formation of an oxide film or the like that inhibits the adhesion of plating on the surface of the Cr coating layer is suppressed. Therefore, if there is no adverse effect of the oxide film or the like, the provision of the plasma etching device 50 or the ion beam etching device 70 downstream of the Cr vapor deposition device 40 is omitted. What omitted these activation processing devices is a layout along the above-mentioned step (2).
  • the steel sheet on which the Cr coating layer has been formed is separated from the melting plating equipment by the original plate It is also possible to use it as 10.
  • the Cr coating layer should be formed by either electroplating or vacuum evaporation. Can be.
  • the process described above is the case where the Cr coating layer is activated by plasma etching and melted by electroplating, and the process described above is the case where activation by ion beam etching is employed.
  • Plasma etching or ion beam etching of vapor-deposited Cr-plated steel sheets are the above-mentioned steps (3) and (4), respectively.
  • Oxide films and altered layers are often formed on the steel sheet surface. Therefore, the adhesion of the Cr coating layer formed by the Cr vapor deposition device 40 to the underlying steel may not be sufficient.
  • a steel sheet having such a surface state is used as a plating original sheet, it is preferable to activate the steel sheet surface prior to the formation of the Cr coating layer.
  • the above-mentioned step (1) employs plasma etching as the activation treatment, and employs the layout shown in FIG.
  • a plasma etching device 50 is arranged upstream of the Cr vapor deposition device 40.
  • an additional plasma etching apparatus may be additionally arranged downstream of the Cr vapor deposition apparatus 40.
  • the above-mentioned process (1) employs ion beam etching as the activation treatment, and employs the layout shown in FIG.
  • an ion beam etching device 70 is arranged upstream of the Cr vapor deposition device 40.
  • a similar ion beam etching device may be additionally arranged downstream of the Cr vapor deposition device 40.
  • the Cr coating layer When the surface of the Cr coating layer is activated and the original plate 10 is introduced into the plating bath 61 and melted, the Cr coating layer has good wettability to the plating metal and a good plating layer is formed. Is done.
  • the plating layer has a different layer composition depending on the composition and temperature of the plating bath, the thickness of the Cr coating layer, the type of base steel, and other factors.
  • the first layer of A1-Si-Fe system and the second layer of Al-Cr-Si-Fe system A plating layer having a layer configuration in which a third layer L 3 of the L 2 , A 1 -Si system is sequentially laminated is formed.
  • the second layer L 2 is, when immersed C r coated steel sheet in a molten plated bath, C r coating layer is formed by diffusing.
  • the second layer L 2 is, Cr concentration is high, causing exhibiting excellent corrosion resistance, heat resistance.
  • the Cr concentration in the second layer L 2 is 0.7 wt% or more, it becomes remarkable.
  • the Cr concentration can be controlled by adjusting the thickness of the Cr coating layer, the composition of the plating bath, the temperature, and the like.
  • the Cr contained in the second layer L 2 exhibits an action to suppress that Fe is diffused from the substrate steel S.
  • the Fe concentration of the entire plating layer is lowered, and the corrosion resistance is improved while the plating layer is formed via the Cr coating layer having good adhesion and wettability.
  • the workability of the coated steel sheet is also improved. As a result, even if the obtained plated steel sheet is processed, the occurrence of flaking, powdering, etc. is suppressed.
  • the plating layer obtained under the condition where the Cr concentration is high is such that the first layer is A 1—Si—Fe—Cr system, the second layer L 2 is A 1—Cr—Si—Fe system, The layer becomes A 1—S i—Cr system.
  • the first layer L, of the A1-Si-Fe-Cr system has a high A1 concentration and contains Cr, so that it has high corrosion resistance.
  • the Cr concentration is 0.1% when a steel sheet such as ordinary steel that does not contain Cr is used as the plating original sheet. / Satoju If the original plate is made of an alloy steel, stainless steel, or the like containing Cr, the Cr concentration in the first layer L, increases due to the diffusion of Cr from the base steel S. The higher the concentration of Cr contained in the first layer L, the better the corrosion resistance. However, even when a high Cr steel containing 40% by weight of (: r) is used as an original plate, the Cr concentration of the first layer is 5% by weight or less.
  • the second layer L 2 is an alloy layer of A 1-C r one S i-F e system, C r is preferentially concentrated.
  • a 1 concentration is high that if we in addition to C r concentration shows the most excellent corrosion resistance in a three-tier ⁇ L 3.
  • C r concentration in the second layer L 2 can be adjusted by the amount of deposition of C r for be plated. For example, when the Cr coating layer is provided with an adhesion amount of 0.1, the Cr concentration of the second layer L is about 3% by weight. Therefore, for applications requiring high corrosion resistance, the amount of Cr attached should be set high.
  • the third layer L 3 is, A 1 caused by the solidification of the plating bath metals - S i - is C r layer is One also almost the same composition as the C r containing except plated bath. It is also diffused C r in the third layer L 3, which contains a small amount of C r of 0.1 wt% or less. The third layer L 3, since it albeit in small quantities contains a C r, the corrosion resistance is improved.
  • a relatively thick Cr coating layer is formed so that the Cr coating layer remains at the interface between the base steel and the plating layer after plating, or it is melted under conditions where Cr diffusion is suppressed.
  • the first layer is C r system
  • the second layer L 2 is C r one S i-a 1 system
  • the third layer L 3 is a 1- S i- C r system.
  • C r - S i - A 1-based second layer L 2 of the exhibits the effect of maintaining the F e diffused from molten plated bath or the like is segregated, the F e concentration of the third layer L 3 low.
  • the second layer L 2 Cr 30 to 60 wt%, S i: 30 to 60 wt%, F e: 30 wt% or less and the balance A 1 the composition
  • the third layer L 3 S i: 6 to 12 wt%, C r:. 0. 05 ⁇ 0 is preferably 5% by weight and the composition of the balance a 1.
  • the second layer L 2, the first layer L, in conjunction with for improving the corrosion resistance, the C r containing 30 to 60 wt%, the F e content is preferably set to Rukoto 30 wt% or less.
  • S i for inhibiting the growth of the second layer L 2 it is contained 30 to 60 wt% It is preferred.
  • the third layer L 3 together with an excellent corrosion resistance, ductile.
  • the third layer L 3 is extended block the crack, exposing the underlying steel is prevented.
  • the inclusion third layer L 3 0.
  • the Cr in the 05 to 0.5 wt% it is possible to increase the corrosion resistance without impairing the ductility.
  • Corrosion resistance can be expected to improve by containing Si.
  • the third layer L 3 as shown in FIG. 6, it is also possible to disperse Cr one S i-A 1-based alloy particles G of. By the dispersion of the alloy particles G, corrosion inhibition of the third layer L 3 is further improved.
  • the alloy particles G can be prepared by maintaining the temperature of the molten A 1 -Si alloy plating bath high or by setting the immersion time of the plating original plate in the plating bath to be long. it can be precipitated from the layer L 2 side.
  • the plated base sheet is immersed in a bath of molten A1-Si alloy plating.
  • A1 killed steel sheet having a composition of Fe and impurities and a thickness of 0.5 mm and a width of 100 mm was used as the original plate for plating. After degreased and pickled the original plating, hot-dip A 1—Si plating was performed using the hot-dip plating apparatus shown in FIG.
  • the vacuum chamber 20 was evacuated to 1 ⁇ 10 ⁇ 3 Pa by the vacuum pumps 22 and 23. After the inside of the vacuum chamber 20 reached a predetermined degree of vacuum, the high-frequency heating device 30, the Cr vapor deposition device 40, and the plasma etching device 50 were operated. The introduction of the raw material gas at this time reduced the degree of vacuum in the vacuum chamber 20 to 3 Pa. Table 1 shows the plasma etching conditions.
  • the resulting multilayer alloy plated steel sheet A 1 of the high content primary phase A 1 one S i alloy and a mixed layer of S i high content alloy precipitated eutectic third layer L 3 are formed I was Under the third layer L 3, A 1-C r one S i-F e based second layer L 2 and A 1 of the - S i - F e based first layer L of, was formed .
  • Te cowpea in regulating the thickness of the C r coating layer provided by vapor deposition, varying the Cr concentration in the second layer L 2. It was then investigated the relationship thickness Mitodai two layers L 2 of Cr concentration and corrosion resistance of the Cr coating layer.
  • Figure 7 shows the survey results.
  • the corrosion resistance was evaluated by performing a salt water spray test specified in JIS and evaluating a time until a red mackerel having an area ratio of 5% was generated on the test piece surface.
  • the Cr coating is introduced into the vacuum chamber 20 of the melting plating facility shown in FIG. 1 or FIG. when subjected to S i alloy plated similarly as long as C r concentration in the second layer L 2 is 0.7 wt% or more, remarkably excellent as compared with the conventional a 1-S i alloy plated steel sheet It was a multi-layer alloy-plated steel sheet that exhibited high corrosion resistance.
  • Example 2
  • Example 2 The same A1 killed steel as in Example 1 was used as the original plate for plating. Plasma etching was performed under the same conditions as in Table 1 using the fusion plating equipment shown in Fig. 3, and then a Cr coating layer was formed by vacuum evaporation. Next, fusion plating was performed under the conditions shown in Table 4. Table 4: Melting conditions for Al-Si alloy
  • the effect of the combination of Cr coating and fusion plating on corrosion resistance was investigated.
  • the same A1 killed steel as in Example 2 was used for the base plate, and the plating bath composition, the amount of A1-Si alloy deposited, and the like were set to the same conditions as in Example 2.
  • the plating base plate in a molten A 1 -Si alloy plating bath after applying Cr coating in advance with other equipment, pass the Cr coated steel plate through the equipment shown in Fig. 3, After activating the surface of the Cr coating layer by operating the plasma etching apparatus 40 without operating the Cr vapor deposition apparatus 50, the molten A11-Si alloy plating bath was coated with Cr. Steel plate was introduced.
  • Example 2 The same A1 killed steel plate as in Example 1 was used as a base plate for plating. After degreasing and pickling the plating base plate, a Cr coating layer is formed by vacuum evaporation or electroplating, and a fusion plating device equipped with a plasma etching device shown in Fig. 3 or an ion beam shown in Fig. 4 Hot-dip A 1—Si plating was performed using a hot-dip plating apparatus equipped with an etching apparatus. The vacuum pump 20 was evacuated to 1 ⁇ 10-3 Pa by the vacuum pumps 22 and 23.
  • the high-frequency heating device 30 and the plasma etching device 50 or the ion beam etching device 70 were operated to activate the surface of the original plating plate 10. .
  • Ar which is a raw material gas for etching
  • the degree of vacuum dropped to 0.05-5 Pa.
  • the plating original plate 10 When Cr coating is applied to the plating original plate 10 by the Cr vapor deposition device 40, the plating original plate 10 is heated by the high frequency heating device 30 prior to vapor deposition, and the plasma etching device 50 or ion beam etching is performed. Since the surface was activated by the apparatus 70, a Cr vapor-deposited layer having a uniform thickness and excellent adhesion was formed on the surface of the base plate 10 for plating.
  • Plasma etching and ion beam etching were performed under the same conditions as in Tables 1 and 3, respectively.
  • the original plate was immersed in a molten A 1 -Si alloy plating bath at a temperature of 64 (TC or less to produce a coated steel plate.
  • Cr remained, and a plated layer having a multilayer structure was formed as shown in Fig. 5 or 6. 1.
  • a Cr coating layer having a film thickness exceeding 5 wm was provided.
  • the Cr coating layer remained even when the molten A1-Si alloy plating bath at a temperature of 64 CTC or more was used, and the resulting coating layer had the multilayer structure shown in FIG. 5 or FIG.
  • the temperature of the plating bath was 640 ° C. or higher, dispersion of Cr—Si—A1 alloy particles G was observed in the third layer.
  • the composition of the third layer L 3 of the plated layer formed on the surface of the steel sheet were investigated in relation to the composition of the plating bath.
  • Table 9 shows the survey results.
  • the Cr coating layer was formed by vacuum evaporation in Table 9, similar results were obtained when the Cr coating layer was formed by electroplating.
  • two types of plating baths were used, one containing 0.08% by weight of Fe as an impurity and one containing intentionally a large amount of Fe of 2.1% by weight. .
  • the third outermost layer is used.
  • the contained Fe content showed a low value of 0.62% by weight or less. This is because Fe contained in the melting bath segregates in the second layer, and a Cr-Si-A1-Fe alloy layer is formed.
  • the Cr coating layer formed on the steel sheet surface prior to melting plating diffuses into the third layer, and the Cr content of the third layer is about 0.4% by weight.
  • the Cr content of the third layer is the Cr concentration of the third layer itself excluding the dispersed Cr-Si-A1 alloy particles. As described above, since the third layer has a high Cr concentration and a low Fe concentration, the third layer exhibits an excellent anticorrosion action.
  • the cross section of the plated steel sheet of Test No. 4 was subjected to linear analysis by EPMA. As is clear from Fig. 11 showing the analysis results, the first layer of the Cr rich layer derived from the Cr coating layer remains on the surface layer of the base steel. Then, F e is, Cr one S i-A 1-segregated in the second layer L 2 of the Fe-based, A 1- S i- Cr-based third layer L 3 of diffused from molten coating bath and the substrate steel No Fe could be detected. Further, in the portion where Cr- S i one A 1 alloy particles in the third layer L 3 are dispersed, Cr concentration and S i concentration had become locally high.
  • Fig. 12 shows the results of investigation of the relationship between the thickness of the Cr coating layer and the corrosion resistance.
  • the thickness of the Cr coating is 0.1 or more, the corrosion resistance is significantly improved.
  • the Cr-Si-A1 alloy Since the particles were dispersed in the third layer, a sticking layer was formed, and the corrosion resistance was further improved.
  • the excellent corrosion resistance was not affected by the concentration of Fe incorporated in the second layer.
  • the corrosion resistance of a steel sheet on which only Cr was deposited was investigated.
  • the 5% redness generation time was as short as 50 hours or less, and the corrosion resistance was poor.
  • the 5% red ⁇ In less than 00 hours sufficient corrosion resistance was not obtained.
  • the fact that excellent corrosion resistance was secured by securing the Cr concentration in the third layer was the same as when the specimen after Cr coating was activated by ion beam etching.
  • the 5% redness generation time exceeded 3500 hours.
  • the 5% red mackerel generation time similarly exceeded 8500 hours.
  • FIG. 13 shows a comparative example in which the Fe concentration of the above was intentionally increased.
  • A1-Si alloy plating was performed using a Cr-containing plating bath whose composition is shown in Table 11.
  • Fig. 14 shows the results obtained by organizing the corrosion resistance of the obtained plated steel sheets by the thickness of the Cr coating layer formed on the steel sheet surface in advance.
  • the apparatus shown in Fig. 3 was used for Cr coating and A1-Si alloy plating. Further, the corrosion resistance was evaluated by a salt spray test under the same conditions as in Example 1.
  • the plated steel sheet has better corrosion resistance than the plating layer obtained from the plating bath that does not contain Cr. It can be seen that is obtained. Microscopic observation of the plated layer of the plated steel sheet revealed that Cr—Al—Si alloy particles dispersed in the third layer had increased. Further improvement in corrosion resistance is due to the increase in Cr-A1-Si alloy particles. It is presumed that there is a cause., Table 11: Plating conditions when using Cr-containing molten A 1 -Si plating bath
  • a Cr coating layer is previously formed on the surface of a steel plate to be plated, and this Cr coating layer is used as a Cr supply source for the plating layer. Also, by removing the oxide film formed on the surface of the Cr coating layer by plasma etching, ion beam etching, or the like, or by continuously performing Cr evaporation and hot-dip plating in the same vacuum atmosphere, r With the coating layer exhibiting good wettability to the plated metal, the original plating plate is immersed in the bath. Therefore, the formed adhesion layer has excellent corrosion resistance and heat resistance by containing Cr, and also has good adhesion to the underlying steel.
  • the plating layer has a different multi-layer configuration depending on the thickness of the Cr coating layer, plating conditions, and the type of plating base plate. Regardless of the multi-layered plated steel sheet, due to the inclusion of Cr, it exhibits significantly superior corrosion resistance and heat resistance as compared with conventional hot-dip A 1 -Si alloy steel sheet. In this way, it has excellent corrosion resistance and heat resistance, Materials are obtained that are used in a wide range of temples.
  • the plating process and the fusion plating equipment are simplified, and a product with low cost and high corrosion resistance and heat resistance can be obtained.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating With Molten Metal (AREA)
  • Physical Vapour Deposition (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
PCT/JP1993/000163 1992-02-12 1993-02-09 TOLE D'ACIER PLAQUEE Al-Si-Cr, AYANT UNE EXCELLENTE RESISTANCE A LA CORROSION, ET PRODUCTION DE CETTE TOLE WO1993016210A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1019930703118A KR0166099B1 (ko) 1992-02-12 1993-02-09 내식성이 우수한 알루미늄-규소-크롬계 도금강판 및 그 제조방법
DE69305458T DE69305458T2 (de) 1992-02-12 1993-02-09 A1-Si-Cr-BESCHICHTETE STAHLPLATTE UND DEREN HERSTELLUNG
EP93903330A EP0584364B1 (de) 1992-02-12 1993-02-09 A1-Si-Cr-BESCHICHTETE STAHLPLATTE UND DEREN HERSTELLUNG
CA002107560A CA2107560C (en) 1992-02-12 1993-02-09 Al-si-cr-plated steel sheet excellent in corrosion resistance and production thereof

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JP4/59016 1992-02-12
JP4/59017 1992-02-12
JP4059017A JPH05222519A (ja) 1992-02-12 1992-02-12 Ｃｒを含有する溶融めっき鋼板の製造方法
JP4059016A JP2938658B2 (ja) 1992-02-12 1992-02-12 多層合金めっき鋼板及びその製造方法
JP7356092 1992-02-25
JP4/73560 1992-02-25
JP5034759A JPH06228725A (ja) 1993-01-29 1993-01-29 溶融Ａｌ−Ｓｉ−Ｃｒ系めっき鋼板及びその製造方法
JP5/34759 1993-01-29
JP03476093A JP3207958B2 (ja) 1992-02-25 1993-01-29 複合Ａｌ合金めっき鋼板及びその製造方法
JP5/34760 1993-01-29

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US9901892B2 (en) 2012-12-13 2018-02-27 General Electric Company Anticoking catalyst coatings with alumina barrier layer

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CN1209481C (zh) * 1995-02-24 2005-07-06 日新制钢株式会社 热镀铝钢板及其制造方法和合金层控制装置
DE102006033072B4 (de) * 2006-07-14 2008-11-13 Von Ardenne Anlagentechnik Gmbh Verfahren und Vorrichtung zum Beschichten von Substraten durch Tauchen in eine Metallschmelze
WO2020188321A1 (en) * 2019-03-20 2020-09-24 Arcelormittal A coated steel substrate, a method for the manufacture of a coated steel substrate, a method for manufacture of a steel product and a steel product

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JPS5576017A (en) * 1978-12-04 1980-06-07 Kawasaki Steel Corp Surface reforming device of continuously annealed steel hoop
JPS5858261A (ja) * 1981-10-01 1983-04-06 Nippon Kokan Kk <Nkk> 連続溶融めつきラインの鋼ストリツプの還元促進方法及び装置
JPH0428852A (ja) * 1990-05-25 1992-01-31 Nisshin Steel Co Ltd 溶融めっき鋼帯の製造方法およびその装置

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US3656919A (en) * 1965-11-01 1972-04-18 Avco Corp Composite metal having a nickel alloy base with a diffused coating
JPS5811770A (ja) * 1981-07-14 1983-01-22 Nippon Steel Corp 耐食性およびメツキ密着性のよい溶融アルミニウムメツキ鋼板の製造法
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FR2664617B1 (fr) * 1990-07-16 1993-08-06 Lorraine Laminage Procede de revetement d'aluminium par trempe a chaud d'une bande d'acier et bande d'acier obtenue par ce procede.

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JPS5576017A (en) * 1978-12-04 1980-06-07 Kawasaki Steel Corp Surface reforming device of continuously annealed steel hoop
JPS5858261A (ja) * 1981-10-01 1983-04-06 Nippon Kokan Kk <Nkk> 連続溶融めつきラインの鋼ストリツプの還元促進方法及び装置
JPH0428852A (ja) * 1990-05-25 1992-01-31 Nisshin Steel Co Ltd 溶融めっき鋼帯の製造方法およびその装置

Cited By (1)

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Publication number Priority date Publication date Assignee Title
US9901892B2 (en) 2012-12-13 2018-02-27 General Electric Company Anticoking catalyst coatings with alumina barrier layer

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KR0166099B1 (ko) 1999-01-15
CA2107560C (en) 1999-05-04
DE69305458T2 (de) 1997-03-06
EP0584364A1 (de) 1994-03-02
DE69305458D1 (de) 1996-11-21

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