Classifications

• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
  • C25D11/02—Anodisation
  • C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
• • 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
  • C23C22/07—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 containing phosphates
  • C23C22/08—Orthophosphates
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
  • C25D5/48—After-treatment of electroplated surfaces

Definitions

• the present invention relates to a method for producing a Zn—Ni alloy with excellent breathability.
• Zn-Ni alloy-plated steel sheets have a corrosion resistance of 5 to 10 times that of Zn-plated steel sheets with the same amount of adhesion.
• Prevention of premature corrosion of automobile body by the use of steel sheets The usage of steel sheets has increased, and the parts to be used have been changed from front-end to front-end bridges and bridges. It has spread to a wide variety of people.
• the steel plate used is a single-sided steel plate with the aim of providing a protective effect (a perforation-preventing effect) in areas where the paint is not sufficiently distributed, such as the inner surface of an automobile body in the early days.
• the steel sheet has been shifting to double-sided steel sheets with the aim of improving the corrosion resistance (prevention of the outer surface) after peeling off the paint film after splashing pebbles etc. on the outer surface of the car body. is there.
• the plating surface often becomes the inside of the bonnet during breath processing, in other words, the extended surface becomes the overhang surface during blessing.
• the effect on the brace formability of the plating surface was small.
• This method makes use of the bounding of the upper Z ⁇ — Ni layer.
• the separated powder adheres to the mold of the breath, so that it is difficult to form a large number of samples. It is not practical because it causes Disclosure of the invention
• the invention of wood is intended to solve the problem of press formability reduction based on the frictional resistance of the plated surface of a Zn-Ni alloy-plated steel sheet.
• the purpose of the present invention is to improve the press formability without accompanying the coating layer.
• a method for manufacturing a steel sheet is provided.
• Z n - applying-out n i alloy dark, H 2 P 0 HP 0 4 2 thereafter - Breath characterized that you anodizing the dark-out surfaces and have ⁇ a solution containing one or both of the ions A method for producing a ⁇ -Ni alloy-plated steel sheet having excellent formability is provided.
• FIG. 1 is a graph of LDR showing the effect of the present invention after immersion treatment.
• FIG. 2 is a graph showing the change in LDR after the immersion treatment.
• Fig. 3 is a graph showing a comparison of LDR between the Zn-Ni alloy-plated sheet and the cold-rolled sheet.
• Fig. 4 is a schematic diagram of a cylindrical deep drawing tester.
• Fig. 5 is a schematic diagram of a sliding resistance tester.
• FIG. 6 is a diagram showing a difference in sliding resistance between a Zn-Ni alloy-plated plate and a cold-rolled plate.
• Figure 3 shows the difficulty of breathability of cold-rolled sheet, single-sided Zn-Ni alloy-plated steel sheet, and double-sided Zn-Ni alloy-plated steel sheet.
• the critical drawing ratio is determined by changing the blank diameter between 60 and 80 mm ⁇ using a cylindrical deep drawing tester as shown in Fig. 4 and using a punch to break the plate. It was measured by taking the ratio of diameter to blank diameter.
• the oil used was Duff 21 Oil Coat Z5 (trade name), a fire protection oil manufactured by Idemitsu Kosan Co., Ltd.
• the steel sheet grade was used to observe only the effect of the plating layer. Is constant (equivalent to SPCC).
• the basis weight per one side of the plating layer was 30 g Zm 2 , and the Ni content was 12.5%.
• the LDR of the double-sided plate is smaller than that of the cold-rolled plate, and the formability is several steps worse.
• the plated steel sheet is an alternative to cold-rolled sheet, it is pressed with a press type designed for cold-rolled sheet, but it is designed especially on the assumption that ultra-deep drawn steel sheet is used. In the breath type, the plate was broken and broken.
• FIG. 5 shows the shape of the test machine used. This tester pulls the sample at a constant speed across the sample, and evaluates the magnitude of the frictional force on the surface based on the magnitude of the load required at that time. The test was performed without oil coating.
• Figure 6 shows the test results.
• Figure 1 shows the change in LDR when the Zn-Ni alloy-plated plate was immersed in the following solution for 4 seconds.
• the basis weight per side of the plate used was 30 gm Ni, the content was 12.5%, and the type used was SPCC.
• Solution used for the immersion process H 2 P0 4 - I on-, HP0 4 2 - may be either including hand or both I on-.
• Suitable Was 1 0 soaking temperature ho in a short time processing of the sub-second is 4 0- e C or more, the concentration of Hitasai liquid H 2 P0 4 - and HP0 4 2 _ a total of 1 O 0 g Roh or preferred - 0
• the metal plate used should have a Ni content of 10 to 17 wt%, preferably 11 to 15%. At less than 10%, this treatment method has no effect, and at more than 17%, the Zn—N i plating layer is apt to cause powdering, and is therefore an object of the present invention.
• the Ni content of the Zn-Ni alloy-coated steel sheet is limited to 10 to 17 wt%.
• Co, Fe, Cr, Cu, Mn, AJ £, and the like are added to the plating alloy layer of the present invention in order to further improve the corrosion resistance. Does not detract from the spirit of the present invention.
• the pH of the solution is preferably from 4 to about I0. If the value is less than 4, the dissolution of Zn particularly in the plating layer becomes severe, and the amount of adhesion of the plating decreases greatly, which is not practical.If the value exceeds 10, the effect of improving the breathability is lost.
• the pH of the solution was limited to 4-10.
• the positive ion contained in the liquid used is more electric than K +, Na + , Mg 2 + , Ca 2 ⁇ NH 4 + , and AJ £ 3 + Zn and Ni. It should be chemically low. The reason is that when the plating plate is immersed in a liquid containing metal ions, it is electrochemically more active than Zn and Ni. This is because the noble metal may cause a substitution reaction with Z ⁇ and ⁇ i and precipitate on the plating surface, resulting in deterioration of the appearance.
• the amount of P adhered to the plating surface is preferably 0.1 to 5 mg / m 2 in terms of P. 0. 1 mg Roh m ho effect in less than 2 rather than name, 5 mg / m 2 had more than in rather than to preferred because you deterioration chemical conversion treatability
• HP0 4 2 - and or H 2 P0 4 - process that by the solution containing may be a spray process by addition to the solution of the above immersion treatment.
• the conditions at this time should be almost the same as those obtained by immersion treatment.
• anodic treatment may be performed in the above solution in addition to dipping and spraying. Is an anodized conditions, it is l OO c / dm 2 or less. in l OO c Z when dm 2 a exceeds the Ki one because layers Ku is because dissolution of Z n is Naru rather large.
• Table 1 also shows the test steel sheets, their mounting conditions, immersion conditions, and breath formability expressed by LDR.
• the lubricating oil used in all cases was Daphne Oil Coat Z5 (trade name) manufactured by Idemitsu Kosan Co., Ltd., which is used as a protective oil.
• FIG. 2 shows the LDR values of Example 1 and Comparative Examples 1 and 2 to further clarify the effects of the present invention.
• Table 2 shows examples of spraying and anodizing. It can be seen that, similarly to the above-mentioned immersion treatment, a Zn-Ni-alloy-plated steel sheet having stable breathability can be obtained by these treatments.

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• Chemical & Material Sciences (AREA)
• Metallurgy (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Electrochemistry (AREA)
• Mechanical Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Electroplating Methods And Accessories (AREA)
• Shaping Metal By Deep-Drawing, Or The Like (AREA)
• Chemical Treatment Of Metals (AREA)
• Other Surface Treatments For Metallic Materials (AREA)

Priority Applications (2)

Applications Claiming Priority (3)

Publications (1)

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Family Applications (1)

Country Status (5)

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Citations (2)

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• 1988
  • 1988-03-16 JP JP63060575A patent/JPH01234592A/ja active Granted
• 1989
  • 1989-03-15 EP EP89903215A patent/EP0364596B1/en not_active Expired - Lifetime
  • 1989-03-15 DE DE68925858T patent/DE68925858T2/de not_active Expired - Fee Related
  • 1989-03-15 WO PCT/JP1989/000276 patent/WO1989008730A1/ja active IP Right Grant
  • 1989-05-30 CA CA 601174 patent/CA1338621C/en not_active Expired - Fee Related

Patent Citations (2)

Non-Patent Citations (1)

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