WO2010070942A1 - 亜鉛系めっき鋼板およびその製造方法 - Google Patents

亜鉛系めっき鋼板およびその製造方法 Download PDF

Info

Publication number
WO2010070942A1
WO2010070942A1 PCT/JP2009/058426 JP2009058426W WO2010070942A1 WO 2010070942 A1 WO2010070942 A1 WO 2010070942A1 JP 2009058426 W JP2009058426 W JP 2009058426W WO 2010070942 A1 WO2010070942 A1 WO 2010070942A1
Authority
WO
WIPO (PCT)
Prior art keywords
steel sheet
zinc
aqueous solution
oxide layer
galvanized steel
Prior art date
Application number
PCT/JP2009/058426
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
牧水洋一
梶山浩志
藤田栄
吉見直人
多田雅彦
増岡弘之
星野克弥
名越正泰
Original Assignee
Ｊｆｅスチール株式会社
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 JP2008319131A external-priority patent/JP5354165B2/ja
Application filed by Ｊｆｅスチール株式会社 filed Critical Ｊｆｅスチール株式会社
Priority to CA2742354A priority Critical patent/CA2742354C/en
Priority to US13/129,504 priority patent/US20110226387A1/en
Priority to EP09833249.7A priority patent/EP2366812B1/de
Priority to CN2009801454920A priority patent/CN102216493A/zh
Publication of WO2010070942A1 publication Critical patent/WO2010070942A1/ja

Links

Images

Classifications

    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/53—Treatment of zinc 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1241—Metallic substrates
    • 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
    • C23C2/26—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
    • C23C2/36—Elongated material
    • C23C2/40—Plates; Strips
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer

Definitions

  • the present invention relates to a method for stably producing a galvanized steel sheet having a small sliding resistance during press forming and having an excellent press formability, and to a galvanized steel sheet having an excellent press formability.
  • Zinc-based galvanized steel sheets are widely used in a wide range of fields centering on automobile body applications. Zinc-based plated steel sheets for such applications are subjected to press forming and used. However, the zinc-based plated steel sheet has a drawback that the press formability is inferior to that of the cold-rolled steel sheet. This is because the sliding resistance of the galvanized steel sheet in the press die is larger than that of the cold-rolled steel sheet. That is, the galvanized steel sheet is less likely to flow into the press mold at a portion where the sliding resistance between the mold and the bead is large, and the steel sheet tends to break.
  • alloyed hot dip galvanized steel sheets that are subjected to alloying after hot dip galvanizing are superior in weldability and paintability compared to hot dip galvanized steel sheets that are not subjected to alloying. Therefore, it is more suitably used for automobile body applications.
  • An alloyed hot-dip galvanized steel sheet is formed by galvanizing the steel sheet and then heat-treating to form an Fe-Zn alloy phase by causing Fe in the steel sheet and Zn in the plating layer to diffuse and cause an alloying reaction. It has been made.
  • This Fe—Zn alloy phase is usually a film composed of a ⁇ phase, a ⁇ 1 phase, and a ⁇ phase, and as the Fe concentration decreases, that is, in the order of ⁇ phase ⁇ ⁇ 1 phase ⁇ ⁇ phase, hardness and melting point Tends to decrease. For this reason, from the viewpoint of slidability, a coating with a high hardness, a high melting point and a high Fe concentration that is difficult to cause adhesion is effective, and an alloyed hot-dip galvanized steel sheet that places importance on press formability Manufactured with high average Fe concentration.
  • Patent Document 1 and Patent Document 2 disclose that the surface of a zinc-based plated steel sheet is subjected to electrolytic treatment, immersion treatment, coating oxidation treatment, or heat treatment to oxidize mainly ZnO. A technique for improving weldability and workability by forming a film is disclosed.
  • Patent Documents 1 and 2 when the techniques of Patent Documents 1 and 2 are applied to an alloyed hot dip galvanized steel sheet, the surface of the alloyed hot dip galvanized steel sheet is inferior due to the presence of Al oxide, and the surface irregularities are large. In addition, the effect of improving the press formability cannot be obtained stably. That is, since the surface reactivity is low, it is difficult to form a predetermined film on the surface even when electrolytic treatment, immersion treatment, coating oxidation treatment, heat treatment, and the like are performed. The film thickness becomes thin at the portion where the amount of Al oxide is large.
  • Patent Document 3 after hot-dip galvanizing and alloying by heat treatment and further temper rolling, the steel sheet is contacted with an acidic solution having a pH buffering action, held for 1 to 30 seconds, and washed with water.
  • an acidic solution having a pH buffering action held for 1 to 30 seconds, and washed with water.
  • Patent Document 4 As a method for uniformly forming an oxide layer on a surface flat portion of a hot dip galvanized steel sheet that is not subjected to alloying treatment, in Patent Document 4, the hot dip galvanized steel sheet after temper rolling is treated with an acidic solution having a pH buffering action. The method of making it contact, and then washing
  • the present invention provides a production method capable of stably producing a galvanized steel sheet having excellent press formability even in a short time and a galvanized steel sheet having excellent press formability. For the purpose.
  • the inventors of the present invention have made extensive studies to solve the above problems. As a result, the following knowledge was obtained.
  • the acidic solution used in the techniques of Patent Documents 3 and 4 has a pH buffering action for the purpose of promoting the dissolution of zinc. Therefore, it is considered that the increase in pH is delayed and the formation of the oxide layer is delayed.
  • the elution time of zinc is included in the generation time of the oxide film. As a result, it is considered difficult to form a thick oxide film in a short time.
  • the present inventors have devised a technique for generating an oxide film in a shorter time by omitting the zinc elution time by previously containing zinc ions in an aqueous solution for generating an oxide film.
  • the formation of the oxide film was not promoted simply by previously containing zinc ions in the aqueous solution.
  • formation of an oxide film was not promoted even when zinc was contained in the treatment liquid. The reason for this is that, in the techniques of Patent Documents 3 and 4, the reduction of hydrogen ions that occurs simultaneously when zinc elutes increases the pH in the vicinity of the surface and makes it easy to generate zinc oxide.
  • the present inventors have devised a technique for adjusting the pH of the aqueous solution to pH 4 to 6 at which zinc oxide is easily generated. It was also found that when the pH of the treatment solution is 4 to 6, zinc is generated as a hydroxide due to a slight increase in the surface pH caused by slight elution of zinc in the plating film.
  • the present invention has been made based on the above findings, and the gist thereof is as follows.
  • the steel sheet is contacted with an aqueous solution, and after the contact treatment is completed, the oxide layer is formed on the surface of the steel sheet by holding for 1 to 60 seconds and then washing and drying.
  • the aqueous solution for contact-treating the steel sheet contains zinc ions in a zinc ion concentration range of 5 to 100 g / l, has a pH of 4 to 6, and a liquid temperature of 20 to 70.
  • the galvanized steel sheet is a galvanized steel sheet on which a coating containing zinc as a main component is formed, a hot dip galvanized steel sheet (referred to as GI steel sheet for short), an galvannealed steel sheet.
  • GI steel sheet hot dip galvanized steel sheet
  • EG steel plate electrogalvanized steel plate
  • vapor-deposited galvanized steel plate alloy galvanized steel plate containing alloy elements such as Fe, Al, Ni, MgCo and the like.
  • FIG. 1 is a diagram showing a main part of the oxide layer forming treatment equipment used in the examples.
  • FIG. 2 is a schematic front view showing the friction coefficient measuring apparatus.
  • FIG. 3 is a schematic perspective view showing the bead shape and dimensions in FIG.
  • FIG. 4 is a schematic perspective view showing the bead shape and dimensions in FIG.
  • FIG. 5 is a diagram showing the influence of the zinc ion concentration on the oxide film thickness.
  • the steel sheet is contact-treated with an aqueous solution, held for 1 to 60 seconds after completion of the contact processing, and then washed with water and dried, whereby an oxide is formed on the surface of the zinc-based plated steel sheet.
  • the aqueous solution contains zinc ions in a zinc ion concentration range of 5 to 100 g / l, has a pH of 4 to 6, and a liquid temperature of 20 to 70 ° C.
  • an aqueous solution containing a predetermined concentration of zinc ions and having a defined pH and liquid temperature is used as an aqueous solution for contact-treating a steel sheet.
  • the term “after contact treatment” means that after the immersion process is completed in the case of immersion treatment, after the spray process is completed in the case of spray treatment, and after the application step is completed in the case of roll coating. is there.
  • an aqueous solution containing zinc ions as the aqueous solution for contact-treating the steel sheet, it is possible to omit the elution time of zinc.
  • the zinc ion has a zinc ion concentration in the range of 5 to 100 g / l. When the zinc ion concentration is less than 5 g / l, sufficient zinc is not supplied and the oxide layer is not formed.
  • the concentration of sulfuric acid contained in the oxide layer to be formed becomes high, and there is a concern that the treatment liquid is contaminated when the oxide is dissolved in the chemical conversion treatment step performed thereafter.
  • zinc ions as sulfates.
  • sulfate ions are taken into the oxide layer to be formed, which seems to have an effect of stabilizing the oxide layer.
  • the formation of the oxide film is not promoted simply by previously containing zinc ions in the treatment liquid. Therefore, in the present invention, it is necessary to adjust the pH to pH 4 to 6 where zinc oxide is easily generated.
  • the pH of the treatment solution is 4 to 6
  • zinc is generated as a hydroxide by a slight increase in surface pH caused by slight elution of zinc in the plating film.
  • zinc elution time can be omitted and zinc oxide can be produced.
  • zinc ions precipitate in the aqueous solution (formation of hydroxide), and are no longer formed as oxides on the steel sheet surface.
  • the pH is less than 4, as described above, the formation of the oxide layer is hindered due to the delay of the pH increase.
  • the temperature of the aqueous solution is 20 to 70 ° C.
  • the formation reaction of the oxide layer occurs when it is held for a predetermined time after contact with the aqueous solution, it is effective to control the plate temperature at the time of holding in the range of 20 to 70 ° C. If it is lower than 20 ° C., the reaction for forming the oxide layer takes a long time, resulting in a decrease in productivity. On the other hand, when the temperature exceeds 70 ° C., the reaction proceeds relatively quickly, but on the contrary, processing unevenness tends to occur on the surface of the steel sheet.
  • the aqueous solutions used in Patent Documents 3 and 4 are characterized by being acidic and having a pH buffering action.
  • the present invention uses an aqueous solution containing zinc ions, a sufficient oxide layer can be formed even if the pH of the aqueous solution is high and zinc does not sufficiently dissolve. Moreover, it seems that it is advantageous for the formation of the oxide that the pH rises rapidly. Therefore, the pH buffering action is not always essential.
  • zinc is contained in the aqueous solution in contact with the steel sheet surface, an oxide layer excellent in slidability can be stably formed. Therefore, other metal ions, inorganic compounds, and the like are added to the aqueous solution. Even if it contains as an impurity or deliberately, the effect of this invention is not impaired.
  • the amount of the aqueous film formed on the surface of the steel sheet is 30 g / m 2 or less.
  • a liquid film amount of 5 g / m 2 or more is suitable for the purpose of preventing the liquid film from drying.
  • the liquid film formed on the surface of the steel sheet after contacting with the aqueous solution is 5 to 30 g / m 2 .
  • the amount of the aqueous film can be adjusted by a squeeze roll, air wiping or the like.
  • the time from immersing in an aqueous solution to washing with water is 1 to 60 seconds.
  • the holding time is set to 60 seconds or less from the viewpoint of sufficiently exerting the effects of the present invention. From the above, an oxide layer containing zinc as a main component and having an average thickness of 10 nm or more is obtained on the surface of the plated steel sheet of the present invention.
  • the phrase “mainly composed of zinc” means that the metal component contains 50% by mass or more of zinc.
  • the oxide layer in the present invention is a layer made of an oxide and / or hydroxide mainly containing zinc as a metal component.
  • the average thickness of the oxide layer needs to be 10 nm or more. When the average thickness of the oxide layer is reduced to less than 10 nm, the effect of reducing the sliding resistance becomes insufficient. On the other hand, if the average thickness of the oxide layer containing zinc as an essential component exceeds 100 nm, the coating is destroyed during press working, the sliding resistance increases, and the weldability tends to decrease, which is not preferable.
  • a GI steel sheet was prepared by applying hot-dip galvanizing with an adhesion amount per side of 45 g / m 2 and an Al concentration of 0.20 mass%, followed by temper rolling. did. Further, on a cold-rolled steel sheet having a thickness of 0.8 mm, the amount of plating adhesion per side is 45 g / m 2 , the Fe concentration is 10% by mass, and the Al concentration is 0.20 by a conventional alloying hot dip galvanizing method. A GA steel sheet having a mass% plating film formed thereon and further subjected to temper rolling was prepared.
  • the EG steel plate which has a plating film
  • surface is 30 g / m ⁇ 2 > on the cold rolled steel plate with a plate
  • an oxide layer was formed using a processing facility having the configuration shown in FIG.
  • steel plates S such as GI steel plates, GA steel plates and EG steel plates obtained as described above were immersed in aqueous solutions having different treatment liquid compositions, temperatures and pHs shown in Table 1-1 and Table 1-2 in the solution tank 2. .
  • the amount of liquid film on the steel sheet surface was adjusted with the drawing roll 3. The liquid film amount was adjusted by changing the pressure of the squeeze roll.
  • a cleaning tank 1 can be provided in front of the solution layer 2.
  • the aqueous solution in which the immersion treatment was performed in the solution tank 2 was an aqueous solution to which a predetermined amount of zinc sulfate heptahydrate was added for the purpose of adding zinc ions.
  • a solution containing 20 g / L of sodium acetate with a pH adjusted with sulfuric acid was also used for comparison.
  • the holding time until water washing is the time until the liquid film amount is adjusted with the squeezing roll 3 and the cleaning is started in the cleaning tank 7, and is adjusted by changing the line speed. What washed the steel plate immediately after squeezing using the shower water washing apparatus 4 of the side was also produced.
  • the steel sheet produced as described above it is determined whether it has a sufficient appearance as an automobile outer plate, and as a method for simply evaluating the press formability, the measurement of the friction coefficient and the actual formability are further improved.
  • a ball head overhang test was conducted for the purpose of simulating in detail.
  • the measuring method is as follows. (1) Press formability evaluation test (Friction coefficient measurement test) In order to evaluate the press formability, the friction coefficient of each test material was measured as follows. FIG.
  • FIG. 2 is a schematic front view showing the friction coefficient measuring apparatus.
  • a friction coefficient measurement sample 11 collected from a test material is fixed to a sample table 12, and the sample table 12 is fixed to the upper surface of a slide table 13 that can move horizontally.
  • a slide table support base 15 On the lower surface of the slide table 13, there is provided a slide table support base 15 having a roller 14 in contact with the slide table 13 and capable of moving up and down.
  • a first load cell 17 is attached to the slide table support 15.
  • a second load cell 18 is attached to one end of the slide table 13 in order to measure the sliding resistance force F for horizontally moving the slide table 13 along the rail 19 with the pressing force applied. ing.
  • 3 and 4 are schematic perspective views showing the shape and dimensions of the beads used.
  • the bead 16 slides with its lower surface pressed against the surface of the sample 11.
  • the bead 16 shown in FIG. 3 has a width of 10 mm, a length of 12 mm in the sliding direction of the sample, and a lower portion at both ends in the sliding direction is formed by a curved surface having a curvature of 4.5 mmR. It has a plane with a direction length of 3 mm.
  • Ball head overhang test Using a 150 mm ⁇ punch for a 200 x 200 mm sample material, the maximum forming height when a bulge was formed by a hydraulic bulge tester. Was measured. At this time, a wrinkle holding force of 100 Ton was applied for the purpose of preventing the inflow of the material, and the lubricating oil was applied only to the surface in contact with the punch. The used lubricating oil is the same as that in the friction coefficient measurement test described above.
  • oxide layer thickness (oxide film thickness) Using a Si wafer on which a thermally oxidized SiO2 film with a film thickness of 96 nm is formed as a reference material, measure O / K ⁇ X-rays with a fluorescent X-ray analyzer. Thus, the average thickness of the oxide layer in terms of SiO 2 was obtained. The analysis area is 30 mm ⁇ .
  • the test results obtained above are shown in Table 1-1 and Table 1-2. The following items became clear from the test results shown in Table 1-1 and Table 1-2. (1) No. Since 1, 47 and 60 are not treated with a solution, an oxide film sufficient to improve the slidability is not formed on the flat portion, and the coefficient of friction is high. (2) No. 2-4, no. 48-50 and no.
  • 61 to 63 are comparative examples using an acidic solution having a pH buffering action. Although the friction coefficient is low and the maximum formation height is high at 30 seconds or more, the treatment for 10 seconds does not satisfy a sufficient decrease in the friction coefficient and an improvement in the maximum molding height.
  • (3) No. 5 to 7 are comparative examples using an acidic solution having a pH buffering action. It shows a high coefficient of friction.
  • (4) No. 8-10, no. 51-53 and no. 64 to 66 are comparative examples which contain zinc ions but whose amount is less than the range of the present invention. Although the friction coefficient is low and the maximum formation height is high at 30 seconds or more, the treatment for 10 seconds does not satisfy a sufficient decrease in the friction coefficient and an improvement in the maximum molding height. (5) No.
  • No. Nos. 17 to 22 are examples in which the time until the solution film is formed on the steel plate surface and washed with water is changed. No. which was washed with water without holding. No. 17 has a slight decrease in the friction coefficient, whereas No. 17 has a holding time of 1 second or more. In 18 to 22, the friction coefficient is lowered and the overhanging property is stably improved.
  • No. Nos. 23 to 40 are examples in which the treatment liquid temperature was changed. 23 to 25 are not sufficient in improving the friction coefficient and the maximum molding height as compared with the other examples. On the other hand, no. Nos.
  • FIG. 5 shows the numbers in Table 1-1 and Table 1-2. 8-22 and no. 4 is a graph showing the influence of zinc ion concentration on the oxide film thickness using 44 to 46.
  • FIG. 5 when the zinc concentration is 5 g / l or more, the oxide film thickness is sufficiently thick even when the holding time is short (for example, 10 seconds), and the oxide film thickness is thin when the holding time is short. It can be seen that the problem of the present invention is solved.
  • a galvanized steel sheet having excellent press formability with a small sliding resistance during press forming can be stably produced even under short production conditions.
  • the sliding resistance during press forming is small, and excellent press formability can be achieved. Since it is excellent in press formability, it can be applied in a wide range of fields, mainly for automobile body applications.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Coating With Molten Metal (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
PCT/JP2009/058426 2008-01-30 2009-04-22 亜鉛系めっき鋼板およびその製造方法 WO2010070942A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CA2742354A CA2742354C (en) 2008-12-16 2009-04-22 Galvanized steel sheet and method for manufacturing the same
US13/129,504 US20110226387A1 (en) 2008-01-30 2009-04-22 Galvanized steel sheet and method for manufacturing the same
EP09833249.7A EP2366812B1 (de) 2008-12-16 2009-04-22 Herstellungsverfahren für ein galvanisiertes stahlblech
CN2009801454920A CN102216493A (zh) 2008-12-16 2009-04-22 镀锌系钢板及其制造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008319131A JP5354165B2 (ja) 2008-01-30 2008-12-16 亜鉛系めっき鋼板の製造方法
JP2008-319131 2008-12-16

Publications (1)

Publication Number Publication Date
WO2010070942A1 true WO2010070942A1 (ja) 2010-06-24

Family

ID=42269468

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/058426 WO2010070942A1 (ja) 2008-01-30 2009-04-22 亜鉛系めっき鋼板およびその製造方法

Country Status (6)

Country Link
EP (1) EP2366812B1 (de)
KR (1) KR20110073573A (de)
CN (1) CN102216493A (de)
CA (1) CA2742354C (de)
TW (1) TWI516638B (de)
WO (1) WO2010070942A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012119973A1 (de) * 2011-03-08 2012-09-13 Thyssenkrupp Steel Europe Ag Stahlflachprodukt, verfahren zum herstellen eines stahlflachprodukts und verfahren zum herstellen eines bauteils

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150014517A (ko) * 2012-07-18 2015-02-06 제이에프이 스틸 가부시키가이샤 화성 처리성 및 내형골링성이 우수한 강판의 제조 방법
WO2019073274A1 (en) 2017-10-12 2019-04-18 Arcelormittal PROCESS FOR PROCESSING METAL SHEET AND METAL SHEET TREATED USING THE SAME
WO2019073273A1 (en) * 2017-10-12 2019-04-18 Arcelormittal PROCESS FOR PROCESSING METAL SHEET AND METAL SHEET TREATED WITH THIS METHOD

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5360332A (en) 1976-11-10 1978-05-30 Nippon Steel Corp Alloyed zincciron plate having excellent weldability
JPH02190483A (ja) 1989-01-19 1990-07-26 Nippon Steel Corp プレス成形性に優れた亜鉛めっき鋼板
JP2000328220A (ja) * 1999-05-18 2000-11-28 Sumitomo Metal Ind Ltd 亜鉛系めっき鋼板およびその製造方法
JP2003306781A (ja) 2002-04-18 2003-10-31 Jfe Steel Kk 合金化溶融亜鉛めっき鋼板の製造方法
JP2004003004A (ja) 2002-04-18 2004-01-08 Jfe Steel Kk プレス成形性に優れた溶融亜鉛めっき鋼板とその製造方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6528182B1 (en) * 1998-09-15 2003-03-04 Sollac Zinc coated steel plates coated with a pre-lubricating hydroxysulphate layer and methods for obtaining same
WO2001081646A1 (fr) * 2000-04-24 2001-11-01 Nkk Corporation Tole d'acier recuit apres galvanisation et procede de production correspondant
KR100707255B1 (ko) * 2003-04-18 2007-04-13 제이에프이 스틸 가부시키가이샤 프레스 성형성이 우수한 용융아연 도금강판과 그 제조방법
CN1846011B (zh) * 2003-08-29 2011-06-08 杰富意钢铁株式会社 热镀锌钢板及其制造方法
FR2864552B1 (fr) * 2003-12-24 2006-07-21 Usinor Traitement de surface par hydroxysulfate
US8268095B2 (en) * 2006-05-02 2012-09-18 Jfe Steel Corporation Method of manufacturing hot dip galvannealed steel sheet and hot dip galvannealed steel sheet
JP5239570B2 (ja) * 2007-09-04 2013-07-17 Ｊｆｅスチール株式会社 亜鉛系めっき鋼板

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5360332A (en) 1976-11-10 1978-05-30 Nippon Steel Corp Alloyed zincciron plate having excellent weldability
JPH02190483A (ja) 1989-01-19 1990-07-26 Nippon Steel Corp プレス成形性に優れた亜鉛めっき鋼板
JP2000328220A (ja) * 1999-05-18 2000-11-28 Sumitomo Metal Ind Ltd 亜鉛系めっき鋼板およびその製造方法
JP2003306781A (ja) 2002-04-18 2003-10-31 Jfe Steel Kk 合金化溶融亜鉛めっき鋼板の製造方法
JP2004003004A (ja) 2002-04-18 2004-01-08 Jfe Steel Kk プレス成形性に優れた溶融亜鉛めっき鋼板とその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012119973A1 (de) * 2011-03-08 2012-09-13 Thyssenkrupp Steel Europe Ag Stahlflachprodukt, verfahren zum herstellen eines stahlflachprodukts und verfahren zum herstellen eines bauteils
EP2683848B1 (de) * 2011-03-08 2020-11-04 ThyssenKrupp Steel Europe AG Verwendung eines stahlflachprodukts für die umformung zu einem bauteil durch warmpressformen und verfahren zur herstellung eines warmpressgeformten bauteils

Also Published As

Publication number Publication date
TW201024461A (en) 2010-07-01
KR20110073573A (ko) 2011-06-29
CA2742354C (en) 2014-02-25
EP2366812A4 (de) 2012-04-25
EP2366812A1 (de) 2011-09-21
EP2366812B1 (de) 2019-08-14
CA2742354A1 (en) 2010-06-24
CN102216493A (zh) 2011-10-12
TWI516638B (zh) 2016-01-11

Similar Documents

Publication Publication Date Title
JP3807341B2 (ja) 合金化溶融亜鉛めっき鋼板の製造方法
JP5044976B2 (ja) 合金化溶融亜鉛めっき鋼板の製造方法および合金化溶融亜鉛めっき鋼板
JP5354165B2 (ja) 亜鉛系めっき鋼板の製造方法
JP5071065B2 (ja) 合金化溶融亜鉛めっき鋼板の製造方法および合金化溶融亜鉛めっき鋼板
WO2010070942A1 (ja) 亜鉛系めっき鋼板およびその製造方法
JP4517887B2 (ja) 溶融亜鉛めっき鋼板の製造方法および溶融亜鉛めっき鋼板
JP4529592B2 (ja) 合金化溶融亜鉛めっき鋼板の製造方法および合金化溶融亜鉛めっき鋼板。
JP5347295B2 (ja) 亜鉛系めっき鋼板およびその製造方法
JP5044924B2 (ja) 合金化溶融亜鉛めっき鋼板の製造方法および合金化溶融亜鉛めっき鋼板
WO2010070943A1 (ja) 亜鉛系めっき鋼板およびその製造方法
JP5593601B2 (ja) 合金化溶融亜鉛めっき鋼板およびその製造方法
JP4525252B2 (ja) 合金化溶融亜鉛めっき鋼板の製造方法
JP4826486B2 (ja) 合金化溶融亜鉛めっき鋼板の製造方法
JP4998658B2 (ja) 合金化溶融亜鉛めっき鋼板の製造方法
JP5386842B2 (ja) 亜鉛系めっき鋼板およびその製造方法
JP5354166B2 (ja) 亜鉛系めっき鋼板の製造方法
JP5163218B2 (ja) 亜鉛系めっき鋼板の製造方法
JP4604712B2 (ja) 溶融亜鉛めっき鋼板の製造方法および溶融亜鉛めっき鋼板
JP5163217B2 (ja) 亜鉛系めっき鋼板の製造方法
JP2008285707A (ja) 亜鉛系めっき鋼板
JP2013181217A (ja) 亜鉛系めっき鋼板の製造方法

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200980145492.0

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09833249

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2742354

Country of ref document: CA

Ref document number: 1772/KOLNP/2011

Country of ref document: IN

ENP Entry into the national phase

Ref document number: 20117010906

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2009833249

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 13129504

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE