Classifications

• • 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
  • C25D5/34—Pretreatment of metallic surfaces to be electroplated
  • C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
  • B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
  • C21D1/26—Methods of annealing
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D6/00—Heat treatment of ferrous alloys
  • C21D6/005—Heat treatment of ferrous alloys containing Mn
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D6/00—Heat treatment of ferrous alloys
  • C21D6/008—Heat treatment of ferrous alloys containing Si
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
  • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
• • 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
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F17/00—Multi-step processes for surface treatment of metallic material involving at least one process provided for in class C23 and at least one process covered by subclass C21D or C22F or class C25
• • C—CHEMISTRY; METALLURGY
  • 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
  • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
  • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
  • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
  • C23G1/08—Iron or steel
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D3/00—Electroplating: Baths therefor
  • C25D3/02—Electroplating: Baths therefor from solutions
  • C25D3/22—Electroplating: Baths therefor from solutions of zinc
• • 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
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D7/00—Electroplating characterised by the article coated
  • C25D7/06—Wires; Strips; Foils
  • C25D7/0614—Strips or foils
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
  • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
  • C25F1/02—Pickling; Descaling
  • C25F1/04—Pickling; Descaling in solution
  • C25F1/06—Iron or steel
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
  • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
  • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
  • C21D8/0236—Cold rolling

Definitions

• the present invention relates to a method for producing a high-strength cold-rolled steel sheet having excellent chemical conversion properties and post-painting corrosion resistance.
• alloy elements such as Si and Mn are added to strengthen the solution or refine crystal grains, and precipitate forming elements such as Nb, Ti, and V are added.
• Effective methods include precipitation strengthening and a method of strengthening by generating a hard transformation structure such as a martensite phase.
• Si is an effective element for increasing the strength while ensuring ductility because Si is less affected by the decrease in ductility than other elements. For this reason, it is almost essential to add Si to a steel sheet that achieves both workability and high strength.
• Si has an extremely low equilibrium oxygen partial pressure of oxide, and is easily oxidized even in a reducing atmosphere in a continuous annealing furnace used in the production of a general cold-rolled steel sheet. For this reason, when a steel sheet containing Si is passed through a continuous annealing furnace, Si is selectively oxidized on the surface of the steel sheet to form SiO 2 . When a steel sheet having SiO 2 formed on the surface is subjected to a chemical conversion treatment before coating, this SiO 2 inhibits the reaction between the chemical conversion treatment liquid and the steel plate. For this reason, in the location where SiO 2 exists, there is a so-called “ske” portion on the surface of the steel sheet where the chemical conversion crystal formed by the chemical conversion treatment is not formed.
• the steel plate in which scales exist after the chemical conversion treatment may already have rust in the water washing stage after the chemical conversion treatment. Even if the rust does not occur, a steel sheet with a scale after chemical conversion treatment has a very poor corrosion resistance after the electrodeposition coating. Therefore, it is very difficult to use a high-strength cold-rolled steel sheet containing Si for body use.
• Patent Document 1 discloses a cold-rolled steel sheet on which an oxide having an atomic ratio [Si / Mn] of 1 or less is formed on the surface, and, as a manufacturing method thereof, [Si / Mn] ratio of steel sheet components, annealing temperature, The thing which prescribed
• Patent Document 1 cannot be applied to a steel sheet containing about 1.0% of Si, which is the mainstream of current high-strength cold-rolled steel sheets.
• Patent Document 2 discloses that the size of Si—Mn composite oxide on the surface of the steel sheet and the number per unit area with respect to the steel sheet of Si: 0.05-2% and [Si] / [Mn] ⁇ 0.4.
• a high-strength cold-rolled steel sheet has been proposed that defines a steel sheet surface coverage of an oxide mainly composed of Si.
• [Si] and [Mn] mean the respective contents.
• Patent Document 3 discloses that [Mn / Si] of the Mn—Si composite oxide on the steel sheet surface with respect to the steel sheet of Si: 0.1 to 1% and [Si] / [Mn] ⁇ 0.4.
• a high-strength cold-rolled steel sheet has been proposed in which the ratio, size, number per unit area, and steel sheet surface coverage of an oxide mainly composed of Si are defined. Further, Patent Document 4 discloses that [Mn / Si] of the Mn—Si composite oxide on the steel sheet surface with respect to the steel sheet of Si: 0.1 to 2% and [Si] / [Mn] ⁇ 0.4.
• a high-strength cold-rolled steel sheet has been proposed in which the ratio, size, number per unit area, and steel sheet surface coverage of an oxide mainly composed of Si are defined. These hold even for steel sheets containing up to 2% Si.
• Patent Document 5 discloses a cold-rolled steel sheet that defines the surface coverage of the Si-based oxide on the steel sheet surface with respect to a steel sheet of Si: 0.4% or more and [Si] / [Mn] ⁇ 0.4.
• a manufacturing method for pickling after annealing has been proposed.
• Patent Document 6 proposes a technique of grinding a steel plate surface by 2.0 g / m 2 or more after annealing with respect to a steel plate containing 0.5 mass% or more of Si.
• Patent Document 7 discloses that after annealing a steel sheet containing Si: 0.5 to 2.0%, it is treated with an acidic solution having a pH of 0 to 4 and a temperature of 10 to 100 ° C.
• Patent Document 5 it is necessary to use a high concentration acid in order to remove the Si-based oxide.
• Patent Documents 6 and 7 it is necessary to provide a section for grinding or an alkaline solution treatment from an acidic solution treatment in the line. For this reason, the techniques described in Patent Documents 6 and 7 lead to an increase in equipment length and cost, and are not realistic.
• Patent Document 8 has both a galling resistance and a chemical conversion treatment property by having a galvanized film having an adhesion amount of 10 to 2000 mg / m 2 on the surface of the steel sheet and having a predetermined crystal orientation.
• Technology has been proposed. This technology was made mainly to improve mold galling resistance.
• chemical conversion treatment even with a small amount of zinc, microcells were formed between the zinc adhesion part and the exposed steel sheet part. This suggests that the chemical conversion reaction becomes active.
• Si concentration of the steel plate is high, a considerable steel plate surface is covered with SiO 2 oxide, and when this portion is a steel plate exposed portion, it cannot be said that microcells are necessarily formed.
• Japanese Patent Laid-Open No. 04-276060 Japanese Patent No. 3934604 JP 2005-290440 A Japanese Patent No. 3889768 JP 2004-323969 A JP 2003-226920 A JP 2007-009269 A JP 2006-299351 A
• An object of the present invention is to provide a method for producing a cold-rolled steel sheet that solves the above-described problems in a high-strength cold-rolled steel sheet containing Si as a strengthening element and has excellent chemical conversion property and corrosion resistance after coating.
• the present inventors pay attention to the fact that when SiO 2 is formed on the surface of the steel sheet, it is difficult to form a chemical conversion crystal because Fe does not dissolve in this portion, and it is possible to form a chemical conversion crystal by some method. I thought it would lead to Therefore, the present inventors pay attention to a zinc phosphate film, which is a kind of general chemical film (a film composed of chemical crystals), and provides thin Zn that forms a chemical film on the surface of a cold-rolled steel sheet. By doing so, it was considered that a zinc phosphate coating could be formed after the chemical conversion treatment, and various studies were conducted.
• the present inventors have further studied, and after performing pickling so as to reduce the weight of the steel sheet after annealing to 0.5 g / m 2 or more, further applying electrogalvanization.
• the present inventors have found that a chemical conversion film can be densely and uniformly formed on any high-Si cold-rolled steel sheet. Specifically, the present invention provides the following.
• a method for producing a high-strength cold-rolled steel sheet containing 0.5 to 2.0% by mass of Si in which the steel sheet is annealed in a non-oxidizing atmosphere and then pickled to 0.5 g / an annealing pickling step for dissolving m 2 or more and less than 2.0 g / m 2, and an electroplating step for electroplating zinc on the condition that the adhesion amount is 100 to 5000 mg / m 2 on the steel plate surface after pickling
• strength cold-rolled steel plate characterized by having.
• the non-oxidizing atmosphere is obtained by introducing a mixed gas of nitrogen and hydrogen, the hydrogen content in the non-oxidizing atmosphere is 10 vol% or less, and the heat annealing is performed as follows: The method for producing a high-strength cold-rolled steel sheet according to (1), wherein the heating temperature is 900 ° C. or lower.
• the workability of the high-strength cold-rolled steel sheet can be improved.
• the chemical conversion film is formed densely and uniformly in the chemical conversion treatment of the paint base, a high-strength cold-rolled steel sheet that achieves both high strength, workability, and chemical conversion treatment performance can be obtained.
• the high strength cold-rolled steel sheet after the chemical conversion treatment is coated, the high-strength cold-rolled steel sheet is excellent in post-coating corrosion resistance.
• the present invention is a method for producing a high-strength cold-rolled steel sheet containing 0.5 to 2.0% by mass of Si, and includes an annealing pickling process and an electroplating process.
• the annealing pickling step is a step of dissolving the steel sheet surface by 0.5 g / m 2 or more and 2.0 g / m 2 or less by pickling after heat annealing the steel sheet in a non-oxidizing atmosphere.
• the electroplating step is a step of electroplating zinc under the condition that the adhesion amount is 100 to 5000 mg / m 2 on the steel plate surface after pickling.
• % in component composition and concentration means “% by mass” unless otherwise specified.
• the steel sheet of the present invention contains 0.5 to 2.0% Si.
• the steel can be strengthened by solid solution strengthening without compromising the formability.
• a sufficiently high strength can be obtained by setting the Si content to 0.5% or more.
• the Si content 2.0% or less, the deterioration of ductility is small, and the reduction in production efficiency during cold rolling can be prevented.
• elements other than Si are not particularly limited, but the steel sheet used in the present invention preferably contains the following elements in the following ranges.
• the steel plate used in the present invention preferably contains 0.05 to 0.25% of C.
• C is an element that contributes to the formation of retained austenite, bainite, martensite, and the like necessary for strengthening the steel structure.
• the C content is preferably 0.05% or more.
• the C content is preferably limited to 0.25% or less.
• a more preferable C content is 0.05 to 0.10%.
• the steel plate used in the present invention preferably contains 0.5 to 3.0% of Mn.
• Mn the steel can be strengthened by solid solution strengthening, the hardenability of the steel can be improved, and the formation of retained austenite, bainite, and martensite can be promoted.
• the Mn content is preferably 0.5% or more. However, such an effect is saturated when the content of Mn exceeds 3.0% and causes an increase in cost. Therefore, the content of Mn is preferably limited to 3.0% or less. A more preferable Mn content is 1.6 to 2.6%.
• the steel plate used in the present invention preferably contains 0.005 to 0.05% of P.
• P is a solid solution strengthening element and is usually an element effective for obtaining a high-strength cold-rolled steel sheet.
• the P content is preferably 0.005% or more. If the P content exceeds 0.05%, spot weldability may be reduced. A more preferable P content is 0.02 to 0.03%.
• the steel sheet used in the present invention may contain 0.005% or less of S.
• S is precipitated in the steel as MnS, and this precipitate lowers the stretch flangeability of the steel sheet.
• a more preferable content of S is 0.0020% or less.
• the steel sheet used in the present invention preferably contains 0.005 to 0.06% Al.
• Al is an element added as a deoxidizer in the steelmaking stage, and is an effective element for separating non-metallic inclusions that reduce stretch flangeability as slag.
• the Al content is preferably 0.005% or more. If the Al content exceeds 0.06%, cost increases. A more preferable Al content is 0.007 to 0.040%.
• the balance other than the above components is preferably Fe and inevitable impurities.
• inevitable impurities are O, N, and the like.
• O and N are typical inevitable impurities that are inevitably mixed in the stage of melting the steel material.
• N deteriorates the formability of the raw steel plate, so it is desirable to remove and reduce it as much as possible in the steel making process.
• the N content is preferably 0.01% or less, which is substantially harmless.
• a more preferable N content is 0.0040% or less.
• the manufacturing method of said steel plate is not specifically limited, For example, it can manufacture from the molten steel which has the said component composition. More specifically, first, a slab is manufactured by continuous casting or ingot-making from molten steel adjusted to the chemical component range. Subsequently, the obtained slab is cooled and then reheated or hot rolled as it is. Next, the obtained hot-rolled sheet is cooled and wound, pickled, and cold-rolled to obtain a steel sheet having a desired thickness. In addition, a normal method can be used from hot rolling to cold rolling without particularly limiting the conditions.
• the steel sheet is heated and annealed in a non-oxidizing atmosphere, and then the steel sheet surface is dissolved by 0.5 g / m 2 or more by pickling.
• the annealing pickling process will be described.
• the non-oxidizing atmosphere means an atmosphere in which Fe, which is a main component of the steel sheet, does not form an oxide.
• an inert gas such as nitrogen is used in a normal annealing process, the oxygen concentration itself in the atmosphere is not controlled.
• the dew point of the gas used is high, an atmosphere in which Fe is oxidized is formed, and therefore the dew point is 0 ° C. or lower.
• the lower limit of the dew point there is no particular limit on the lower limit of the dew point.
• the lower limit is preferably set to ⁇ 50 ° C.
• the non-oxidizing atmosphere in the present invention is an atmosphere for reducing a thin surface oxide film (Fe-based material) formed in the process up to cold rolling in addition to an atmosphere in which Fe is not oxidized.
• the non-oxidizing atmosphere is preferably a nitrogen gas containing hydrogen.
• the necessary hydrogen ratio is preferably in the range of 0.1 to 10 vol%. This is because if the hydrogen ratio is less than 0.1 vol%, the reduction of the thin surface oxide film may not be sufficient, and even if it exceeds 10 vol%, the effect on the reduction of the surface oxide film does not change.
• the hydrogen concentration is 0.01 vol% or less, if the pickling is not sufficient, the oxide film on the surface is strong and it is difficult to apply Zn plating, and the pickling loss is increased more than other conditions. There is a need.
• the dew point of the atmospheric gas is not particularly limited, and may be set within a general range, and may be set within a range of ⁇ 50 to 0 ° C. What is necessary is just to adjust the dew point of atmospheric gas suitably in the range in which the oxidation of Fe is suppressed.
• the heating temperature is preferably 900 ° C. or lower. Further, from the viewpoint of sufficiently heating the steel sheet by annealing, the heating temperature is preferably set to 700 ° C. or higher. A more preferable heating temperature is 800 to 850 ° C.
• the heating time during the heat annealing (the total of the temperature rising time and the holding time after reaching the maximum steel plate temperature) is not particularly limited. It is preferably 4 minutes or less from the viewpoint of easily controlling the area ratio of the film-like oxide described later. In addition, the heating time is preferably 10 seconds or more from the viewpoint of sufficiently heating the steel sheet by annealing.
• the area ratio described later of the film-like oxide present on the surface of the steel sheet after annealing it is preferable to control the area ratio described later of the film-like oxide present on the surface of the steel sheet after annealing. If the heating temperature and the heating time are within the above ranges, the area ratio of the oxide on the surface of the steel sheet can be easily suppressed within the allowable range.
• the cooling rate and cooling stop temperature in this cooling are not particularly limited, and general conditions can be adopted.
• the range of 5 to 150 ° C./second is common for the cooling rate, and the range of 300 to 500 ° C. is typical for the cooling stop temperature.
• the reaction of the chemical conversion treatment solution etching the steel sheet and precipitating chemical crystals is hindered.
• the steel sheet is inferior in chemical conversion processability.
• the problem of this chemical conversion processability deterioration becomes large.
• the chemical conversion property of a steel plate is improved by the following pickling after heat annealing. Specifically, pickling is performed to dissolve the steel sheet surface by 0.5 g / m 2 or more. The chemical conversion property of the steel sheet surface is improved by dissolving the steel sheet surface by 0.5 g / m 2 or more. In particular, according to the present invention, it is possible to form a good chemical conversion film even on a steel sheet having a surface thickened during annealing.
• the above-described effect in the present invention is due to the following mechanism.
• a steel sheet containing a relatively large amount of easily oxidizable elements such as Si and Mn is annealed, the oxide is concentrated with a certain distribution on the surface.
• This surface-concentrated oxide includes a relatively small granular distribution and a slightly wider film distribution.
• zinc plating is applied by electroplating, zinc is not deposited on the oxide distributed in the form of a film. This is because the oxide that is concentrated on the surface is generally an insulator, and there is a portion that cannot conduct electricity locally. In such a portion, when the steel sheet comes into contact with the chemical conversion treatment solution, Fe does not dissolve, and there is almost no added zinc.
• a dissolution reaction by the treatment liquid occurs also for the galvanization formed in the void immediately below the film-like oxide. It is considered that a uniform and dense chemical film can be formed by depositing chemical crystals starting from Zn in the voids.
• the pickling after annealing has been conventionally performed.
• the above patent document describes that pickling is performed after annealing.
• Patent Documents 2 to 4 describe a technique that mainly forms a larger amount of Si—Mn-based oxide than Si-based oxide and uses the fact that this Si—Mn-based oxide is soluble. In order to assist this, pickling after annealing may be performed.
• the purpose of the pickling in Patent Documents 2 to 4 is as described above, and since it is not assumed that the steel plate surface is melted, it can be said that the pickling is not a pickling that dissolves the steel plate surface by 0.5 g / m 2 or more.
• Patent Documents 5 to 7 describe that strong pickling is mainly performed to remove Si oxide, and Patent Documents 5 and 6 describe that 2 g / Pickling that requires a steel sheet reduction of m 2 or more is required.
• Patent Document 7 describes that an Si-based oxide is removed by treatment with an acid and an alkali, and pickling that requires a steel sheet weight loss of 2.0 g / m 2 or more is required. Further, in Patent Documents 5 to 7, since there is no Si-based oxide on the steel sheet surface, it differs from the structure of the steel sheet surface in the present invention.
• Patent Document 8 also describes a pretreatment using an acid or an alkali prior to electrogalvanization, but this is only for the purpose of cleaning and activation. In the case of pickling for the purpose of washing and activation, it is not necessary to actively dissolve the steel sheet surface, and the pickling loss by pickling is usually about 0.1 g / m 2 .
• the amount of pickling reduction is 0.5 g / m 2 or more. This is because the pickling weight loss of less than 0.5 g / m 2 is insufficient, although it can partially create voids, and the above-described effects cannot be obtained. Moreover, an extremely large amount of pickling loss deteriorates the chemical conversion treatment property, and causes an increase in the length of the equipment and a long processing time, which is not practical. Therefore, the pickling weight loss is less than 2.0 g / m 2. .
• the kind of the acidic liquid used for the pickling is not particularly limited, and nitric acid, hydrofluoric acid, hydrochloric acid, sulfuric acid and the like are preferably used. Among these, use of sulfuric acid is preferable from the viewpoint of work safety and the like.
• the acid concentration of the acidic liquid is not particularly limited, and may be appropriately set, for example, from a range of 5% by mass to 20% by mass.
• the pickling method is not particularly limited, and a general method can be adopted.
• a method of pickling by electrolytic pickling is preferable from the viewpoint of easy control of pickling reduction.
• the pickling loss can be adjusted by changing the energization time with the current density at the time of energization constant, or changing the current density with the energization time constant.
• the following electroplating process is performed to improve the chemical conversion property of the high-strength cold-rolled steel sheet.
• zinc is electroplated on the surface of the steel plate after pickling under the condition that the adhesion amount is 100 to 5000 mg / m 2 .
• the zinc plating applied to the steel sheet surface functions to promote the formation of chemical conversion crystals, so that a sufficient amount of Zn must be present on the steel sheet surface to form a dense and uniform chemical conversion film. From this viewpoint, the lower limit Zn deposition amount is 100 mg / m 2 .
• the upper limit of the adhesion amount is 5000 mg / and m 2.
• electrogalvanization is performed by electrolysis while circulating a plating solution using a steel plate and an insoluble anode as a cathode in a zinc plating bath filled with an acidic plating solution containing a predetermined amount of zinc ions.
• This is a method of forming galvanization on the surface.
• the zinc ion concentration in the plating solution, the types of acidic components in the plating bath, the pH and temperature of the plating bath, the flow rate when circulating the plating solution, and the current density during electrolysis are galvanized with the desired amount of adhesion. If it can form in a steel plate surface, it will not specifically limit.
• Adhesion amount can be adjusted, for example, by changing the current density with a constant energization time or changing the energization time with a constant current density.
• the present invention is characterized in that Zn is precipitated in the voids existing between the film-like Si oxide and the steel plate. It is effective to control the ratio of the voids to the entire area.
• the lower limit adhesion amount of Zn defined in the present invention is the Zn amount capable of covering the entire steel sheet surface. If there is a non-conductive Si-based oxide and a void exists at the interface with the steel sheet as in the present invention, the Zn to be deposited is formed in this void, so that the entire surface of the steel sheet is covered with Zn as a total. Will do.
• the distribution of Zn from the steel sheet surface is measured by a technique such as an electron beam microanalyzer (EPMA) on the assumption that the amount of deposited Zn is within the specified range of the present invention. It can be obtained by analyzing and calculating the area ratio of Zn not detected on the surface. In order to control the area ratio, the area ratio of the film-like Si-based oxide existing on the surface of the steel sheet after annealing may be controlled.
• EPMA electron beam microanalyzer
• the portion where the SiO 2 film is formed on the surface does not conduct electricity, so the Zn layer is not formed. However, if there is a gap between the steel plate and SiO 2 , the Zn layer is formed in this gap. Therefore, the coverage with Zn becomes extremely high.
• the coverage is preferably 100%.
• the area ratio of Zn adhering to the surface is preferably 60% or more, and the area ratio of Zn adhering to the gap (the ratio of the voids) is preferably 40% or less.
• the high-strength cold-rolled steel plate manufactured by the manufacturing method of the present invention is excellent in chemical conversion treatment.
• P-containing aqueous solution a phosphorus-containing aqueous solution
• the high-strength cold-rolled steel sheet after chemical conversion treatment in the present invention is also included in the high-strength cold-rolled steel sheet obtained by the production method of the present invention.
• the P concentration of the aqueous solution brought into contact with the steel plate is not particularly limited.
• the P concentration is preferably 0.001 g / L or more, and is particularly effective when it is in the range of 0.001 to 10 g / L. This is because when the P concentration is less than 0.001 g / L, the washing effect of sulfate radicals is small, and the adhesion of P to the surface is insufficient, and conversely, even if it exceeds 10 g / L, the effect is large. Since no difference is observed, the upper limit is 10 g / L.
• the temperature of the P-containing aqueous solution is not particularly limited, but is preferably 30 ° C.
• the effect by performing a P containing aqueous solution contact process as the said temperature is 30 degreeC or more is fully acquired.
• the upper limit does not exist in terms of whether or not there is an effect, but it is realistic that the upper limit is 80 ° C. from the viewpoint of increasing the temperature in actual line operation.
• the temperature of the P-containing aqueous solution exceeds 60 ° C., the effect is sufficient, but it is not economically appropriate because an extra facility for heating is required. For this reason, it is more preferable that the upper limit of the temperature is 60 ° C.
• the method of bringing the P-containing aqueous solution into contact may be an immersion method or a spray method, and this method is not particularly limited.
• the spray pressure, nozzle diameter, distance from the nozzle to the steel plate, and the like when the spray method is adopted are not particularly limited, as long as the aqueous solution is in contact with the steel plate.
• alkaline degreasing solution examples include silicates such as sodium orthosilicate, sodium metasilicate, No. 1 sodium silicate, and No. 2 sodium silicate, primary sodium phosphate, secondary sodium phosphate, and tertiary phosphate.
• silicates such as sodium orthosilicate, sodium metasilicate, No. 1 sodium silicate, and No. 2 sodium silicate, primary sodium phosphate, secondary sodium phosphate, and tertiary phosphate.
• a liquid having a pH of 9 to 14 containing at least one selected from active agents can be mentioned.
• a film (film composed of phosphate crystals) formed by a chemical conversion treatment performed thereafter can be more uniformly attached.
• the surface conditioning treatment include immersion treatment in a titanium colloid-containing aqueous solution, a zinc phosphate colloid-containing aqueous solution, and the like.
• This zinc phosphate treatment step is a step for forming a chemical conversion film.
• the method of zinc phosphate treatment is not particularly limited.
• a method of immersing a steel sheet in a chemical conversion treatment solution containing zinc phosphate a method of coating the chemical conversion treatment solution with a spray, a coater, or the like.
• the phosphate crystal formed by the chemical conversion treatment is phosphophyllite (Zn 2 Fe (PO 4 ) 2 .4H 2 O), but in the present invention, the phosphate crystal is a hopite (Zn 3 (PO 4 )). A large amount of 2.4H 2 O) is also precipitated.
• P ratio analyzing the steel sheet after chemical conversion treatment by X-ray diffraction, P / (P + H) value when the strength of phosphophyllite is P and the strength of phosphite is H
• P ratio analyzing the steel sheet after chemical conversion treatment by X-ray diffraction, P / (P + H) value when the strength of phosphophyllite is P and the strength of phosphite is H
• the type of paint used for painting is not particularly limited, and can be selected as appropriate according to the application.
• the coating method of the paint is not particularly limited, and examples of the coating method include electrodeposition coating, roll coater coating, curtain flow coating, and spray coating.
• the coating method include electrodeposition coating, roll coater coating, curtain flow coating, and spray coating.
• means such as hot air drying, infrared heating, induction heating and the like can be used.
• the coated steel sheet obtained in this way is also included in the high-strength cold-rolled steel sheet manufactured by the manufacturing method of the present invention.
• Steels A to D having the composition shown in Table 1 are melted by a conventional steelmaking process, continuously cast into a slab, and the slab is reheated to 1250 ° C.
• Hot rolling was performed at 850 ° C. and a coiling temperature of 600 ° C. to obtain a hot rolled sheet having a thickness of 3.0 mm.
• the hot-rolled sheet was pickled and then cold-rolled to a plate thickness of 1.5 mm to obtain a test material.
• This test material was subjected to heat treatment in the range of 800 to 850 ° C. in a nitrogen atmosphere containing 10 vol% of hydrogen using a laboratory reduction heating simulator, and an annealed plate was produced.
• the annealed steel sheet was subjected to electrolytic pickling using a stainless steel plate as a cathode, using a 100 g / L sulfuric acid aqueous solution. At this time, the current density was kept constant at 10 A / dm 2, and the pickling weight loss was changed depending on the energization time.
• the pickled steel sheet contains zinc sulfate heptahydrate: 1 mol / L and is electroplated using an iridium oxide plate on the anode using an aqueous solution adjusted to pH 2.0 with sulfuric acid, Zinc plating was deposited on the surface.
• the amount of zinc deposited in galvanizing was changed by changing the current density and the energization time.
• the P containing aqueous solution contact process was performed after the galvanization.
• the cold-rolled steel sheet thus prepared is subjected to an X-ray microanalyzer (EPMA) analysis at an acceleration voltage of 5 kV, and the abundance ratio (Zn area ratio) in which Zn is not detected is calculated by image processing from the Zn mapping analysis result. did. Moreover, in order to judge the quality of chemical conversion property, the following chemical conversion treatment was implemented.
• EPMA X-ray microanalyzer
• a degreasing solution in which a commercially available alkaline degreasing solution (manufactured by Nihon Parkerizing Co., Ltd., Fine Cleaner FC-E2001) was built at a predetermined concentration, and a bath having a concentration diluted to twice the predetermined concentration in the case of deterioration.
• the steel sheet was immersed in the degreasing solution for 2 minutes, and the water wetting rate of the steel sheet after washing with water was evaluated.
• a sample having a water wettability of 80% or more was designated as “ ⁇ ”, a sample having less than 80% as “ ⁇ ”, and a sample having 50% or less as “x”, and was used as a degreasing index.
• a water wetting rate of 80% or more is considered good.
• the cold-rolled steel sheet degreased with a degreasing solution having a predetermined concentration is immersed in a surface conditioning solution (Nippon Parkerizing Co., Ltd., PL-ZTH), and then a phosphate treatment solution (Nippon Parkerizing Co., Ltd. In PB-L3080), a chemical conversion treatment was performed by immersing in a bath temperature of 43 ° C. and a treatment time of 120 seconds.
• the steel sheet surface after chemical conversion treatment is observed with 10 fields of view at a magnification of 300 using an SEM, and the following five stages are determined depending on the presence / absence and size of a region (skee) where no chemical conversion crystal is generated and the nonuniformity of the crystal state. (Chemical conversion score).
• the minute scale is a size of a circle having a diameter of 10 ⁇ m.
• ED coating (GT-10, manufactured by Kansai Paint Co., Ltd.) was applied at a coating thickness of 20 ⁇ m. After cross-cutting with an NT cutter, warm brine (5% NaCl, 50 ° C.) For 10 days. The sample after the immersion was covered with a polyester tape to cover the cross-cut portion, and after performing the peeling operation, the maximum peeling width on one side from the cut (hot salt water immersion one-side peeling width) was measured. Tables 2 to 4 show the test results.
• the steel sheets that were just annealed were galvanized within the adhesion amount range specified in the present invention, but were not subjected to the pickling specified in the present invention (Comparative Examples 5 to 8), pickling In the examples (Comparative Examples 9 to 12) in which the pickling weight loss is not within the range specified in the present invention even though it is applied, almost no improvement is observed in the determination with respect to the chemical conversion treatment film state and the peeling width after immersion in hot salt water. .
• Example 21 to 24 of the present invention the surface state was changed by making the heating time in annealing longer than normally considered. Comparing these with other invention examples, despite the range of pickling loss and galvanized adhesion specified in the present invention, the chemical formation score is not high, and the peeling width after immersion in hot salt water remains large. From this, it can be seen that it is necessary to take into account the area ratio of Zn distribution on the surface as well as the amount of adhesion.
• the degreasing liquid as it is built is sufficient. Although a good degreasing property was obtained, water repelling occurred after degreasing in the diluted solution simulating the deterioration state in an actual coating line. Similarly, even in cases where the P concentration was high and the treatment liquid temperature was low (Example 43 of the present invention), the diluted degreasing liquid did not provide sufficient degreasing properties. In contrast, in the examples where the P concentration and the treatment liquid temperature were within the scope of the present invention (Invention Examples 39 to 42, 44 to 48), sufficient degreasing properties were obtained even with the diluted degreasing liquid.
• the chemical conversion treatment property before coating is good and the corrosion resistance after coating is also good, so that it can be applied as an automobile body application.

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• 2013
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